CN102076781A - 新型有机染料及其制造方法 - Google Patents
新型有机染料及其制造方法 Download PDFInfo
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- CN102076781A CN102076781A CN2009801250355A CN200980125035A CN102076781A CN 102076781 A CN102076781 A CN 102076781A CN 2009801250355 A CN2009801250355 A CN 2009801250355A CN 200980125035 A CN200980125035 A CN 200980125035A CN 102076781 A CN102076781 A CN 102076781A
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- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 161
- 239000000975 dye Substances 0.000 claims abstract description 103
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000000126 substance Substances 0.000 claims description 269
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- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 claims description 32
- 239000004065 semiconductor Substances 0.000 claims description 32
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 27
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 26
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- 239000000758 substrate Substances 0.000 claims description 25
- 206010070834 Sensitisation Diseases 0.000 claims description 17
- 230000008313 sensitization Effects 0.000 claims description 17
- 150000003053 piperidines Chemical class 0.000 claims description 16
- 229910019213 POCl3 Inorganic materials 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
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- NRHMKIHPTBHXPF-TUJRSCDTSA-M sodium cholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 NRHMKIHPTBHXPF-TUJRSCDTSA-M 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- C09B57/008—Triarylamine dyes containing no other chromophores
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- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
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- C—CHEMISTRY; METALLURGY
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- C09B23/14—Styryl dyes
- C09B23/148—Stilbene dyes containing the moiety -C6H5-CH=CH-C6H5
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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Abstract
本发明涉及一种新型有机染料及其制造方法,本发明的染料化合物用于染料敏化太阳能电池(dye-sensitized solar cell,DSSC),比以往的染料显示出更高的摩尔吸光系数、Jsc(短路光电流密度)和光电转换效率,从而可以大幅度提高太阳能电池的效率,并且,不使用昂贵的柱也可以进行精制,从而可以突破性地降低染料合成成本。
Description
技术领域
本发明涉及一种用于染料敏化太阳能电池(dye-sensitized solar cell,DSSC)的新型染料及其制造方法。
背景技术
1991年瑞士国立洛桑高等技术学院(EPFL)的迈克尔格莱才尔(Michael Gratzel)的研究小组开发了染料敏化纳米粒子氧化钛太阳能电池后,进行了很多关于该领域的研究。染料敏化太阳能电池相比于现有的硅系太阳能电池效率高,制造成本显著低,因此,具有能够代替现有的非晶质硅系太阳能电池的可能性,并且,与硅系太阳能电池不同,染料敏化太阳能电池是以能够通过吸收可见光而生成电子-空穴(hole)对的染料分子和传递所生成的电子的过渡金属氧化物作为主要组成材料的光电化学太阳能电池。
作为用于染料敏化太阳能电池的染料广泛使用的是显示出高光电转换效率的钌金属配位化合物,但是该钌金属配位化合物存在价格太贵的缺点。
最近发现,在吸光效率、氧化还原反应稳定性和分子内电荷转移(charge-transfer,CT)系吸收的方面表现出优异物性的、不含有金属的有机染料可以作为能够代替昂贵的钌金属配位化合物的太阳能电池用染料来使用,所以对缺少金属的有机染料的研究正在集中进行。
有机染料一般具有通过π-键单元连接的电子给体(electron donor)-电子受体(electron acceptor)残基的结构。在大部分的有机染料中,胺衍生物起到电子给体的作用,2-氰基丙烯酸酯或绕丹宁残基起到电子受体的作用,这两个部位通过次甲基单元或噻吩链等π-键系统连接。
一般来说,作为电子给体的胺单元的结构变化会带来电子特性的变化,例如获得向蓝色侧位移(shift)的吸收光谱,可以通过改变π-键长度,来调节吸收光谱和氧化还原电位(redox potential)。
但是,目前已知的大部分的有机染料相比于钌金属配位化合物染料表现出低的转换效率和低的驱动稳定性,所以目前正在进行旨在通过改变这样的电子给体和受体的种类或π-键长度,而开发出相比于现有的有机染料化合物具有更高的摩尔吸光系数、并表现出高的光电转换效率的新的染料的努力。
发明内容
技术问题
因此,本发明的目的在于提供一种相比于以往的染料显示出更高的摩尔吸光系数和光电转换效率,从而能够大大提高太阳能电池的效率的有机染料及其制造方法。
另外,本发明的目的在于提供通过含有上述染料,而表现出明显提高的光电转换效率、Jsc(短路光电流密度,short circuit photocurrent density)和摩尔吸光系数优异的染料增感光电转换元件,以及效率明显提高的太阳能电池。
技术方案
为了达到上述目的,本发明提供由下述化学式1表示的有机染料。
[化学式1]
在上述式中,
R1为
或
上述X和Y各自独立地为氢或C1-6烷基;
R2至R5各自独立地为氢、取代或非取代的C1-30烷基或C1-30烷氧基;
Ar为被一个以上的C1-30烷基、C1-30烷氧基、卤素、酰胺基、氰基、羟基、硝基、酰基、C6-30的芳基或杂芳基取代的或者非取代的C6-50的芳基或者杂芳基,优选为
(*部分为结合部分);
Z和Z’各自独立地为C1-6烷基;
n为1至10的整数;
m和m’各自独立地为0至5的整数,m和m’二者不同时为0,优选为1或2。
另外,本发明提供由化学式1-1表示的染料(m’为0的情况)的制造方法,包括:
(1)使下述化学式2的化合物与下述化学式3的化合物进行铃木(Suzuki)偶联反应来制造下述化学式4的化合物,
(2)使化学式4的化合物在有机溶剂中与POCl3反应来制造下述化学式5的化合物,
(3)在CH3CN中,在哌啶存在下,使化学式5的化合物与氰基乙酸或下述化学式6的化合物反应;
[化学式1-1]
[化学式2]
[化学式3]
[化学式4]
[化学式5]
[化学式6]
在上述式中,X、Y、R1至R5、Ar、Z、m和n与上述定义相同。
另外,本发明提供由化学式1-2表示的染料(m’不为0的情况)的制造方法,包括:
(i)使下述化学式2的化合物与下述化学式3的化合物进行铃木偶联反应来制造下述化学式4的化合物,
(ii)使化学式4的化合物在有机溶剂中与N-溴苯乙烯反应来制造下述化学式7的化合物,
(iii)使化学式7的化合物与下述化学式8的化合物进行铃木偶联反应来制造下述化学式9的化合物,
(iv)使化学式9的化合物在有机溶剂中与POCl3反应来制造下述化学式10的化合物;
(v)在CH3CN中,在哌啶存在下,使化学式10的化合物与氰基乙酸或下述化学式6的化合物反应;
[化学式1-2]
[化学式2]
[化学式3]
[化学式4]
[化学式7]
[化学式8]
[化学式9]
[化学式10]
[化学式6]
在上述式中,X、Y、R1至R5、Ar、Z、Z’、m和n与上述定义相同,
a为1至5的整数,优选为1或2。
另外本发明提供一种染料增感光电转换元件,其特征在于,包括担载有由上述化学式1表示的化合物的氧化物半导体微粒。
另外,本发明提供一种染料敏化太阳能电池,其特征在于,包括上述染料增感光电转换元件。
有益效果
本发明的染料化合物用于染料敏化太阳能电池(DSSC),比以往的染料表现出更高的摩尔吸光系数、Jsc(短路光电流密度)和光电转换效率,从而能够大大提高太阳能电池的效率,并且,即使不使用昂贵的柱也能够进行精制,从而可以突破性地降低染料合成成本。
具体实施方式
本发明的发明人们确定将具有新的有机染料结构的由化学式1表示的化合物担载在氧化物半导体微粒上来制造染料敏化太阳能电池的情况下,光电转换效率、Jsc(短路光电流密度)和摩尔吸光系数高,从而显示出比现有的染料敏化太阳能电池优异的效率,从而完成了本发明,其中,上述由化学式1表示的化合物使用2,3-二氢噻吩并[3,4-b][1,4]二噁英,中间连接部分导入用于增加摩尔吸光系数并增加元件的稳定性的噻吩单元,将很好地适用于TiO2改性且电子转移能力最好的氰基丙烯酸作为电子受体。
本发明的有机染料的特征在于由下述化学式1表示,优选具有下述化学式1a至1x的结构。
[化学式1]
[化学式1a]
[化学式1b]
[化学式1c]
[化学式1d]
[化学式1e]
[化学式1f]
[化学式1g]
[化学式1h]
[化学式1i]
[化学式1j]
[化学式1k]
[化学式1l]
[化学式1m]
[化学式1n]
[化学式1o]
[化学式1p]
[化学式1q]
[化学式1r]
[化学式1s]
[化学式1t]
[化学式1u]
[化学式1v]
[化学式1w]
[化学式1x]
在上述式中,R1至R5、Ar、Z、Z’、m、n和m’与上述定义相同。
另外,本发明提供m’为0的由上述化学式1-1表示的染料的制造方法,由化学式1-1表示的染料通过以下方法制造:(1)使下述化学式2的化合物与下述化学式3的化合物进行铃木偶联反应来制造下述化学式4的化合物;(2)使化学式4的化合物在有机溶剂(例如二甲基甲酰胺)中与POCl3反应,制造下述化学式5的化合物;(3)在CH3CN中,在哌啶存在下,使化学式5的化合物与氰基乙酸或下述化学式6的化合物反应。其具体例子可以由下述反应式1至4表示(反应式1:化学式1a的化合物,反应式2:化学式1b的化合物,反应式3:化学式1e的化合物,反应式4:化学式1f的化合物)
[化学式2]
[化学式3]
[化学式4]
[化学式5]
[化学式6]
[反应式1]
[反应式2]
[反应式3]
[反应式4]
在上述式中,R2至R5、X、Y、Ar、Z、m和n与上述的定义相同。
另外,本发明提供m’不为0的由上述化学式1-2表示的染料的制造方法,由化学式1-2表示的染料通过以下方法制造:(i)使下述化学式2的化合物与下述化学式3的化合物进行铃木偶联反应来制造下述化学式4的化合物;(ii)使化学式4的化合物在有机溶剂(例如四氢呋喃)中与N-溴苯乙烯反应来制造下述化学式7的化合物;(iii)使化学式7的化合物与下述化学式8的化合物进行铃木偶联反应来制造下述化学式9的化合物;(iv)使化学式9的化合物在有机溶剂(例如二甲基甲酰胺)中与POCl3反应来制造下述化学式10的化合物;(v)在CH3CN中,在哌啶存在下,使化学式10的化合物与氰基乙酸或下述化学式6的化合物反应。其具体例子可以由下述反应式5至10表示(反应式5:化学式1n的化合物,反应式6:化学式1r的化合物,反应式7:化学式1q的化合物,反应式8:化学式1m的化合物,反应式9:化学式1w的化合物,反应式10:化学式1u的化合物)。
[化学式2]
[化学式3]
[化学式4]
[化学式7]
[化学式8]
[化学式9]
[化学式10]
[化学式6]
[反应式5]
[反应式6]
[反应式7]
[反应式8]
[反应式9]
[反应式10]
在上述式中,R2至R5、X、Y、Ar、Z、Z’、m、n和a与上述的定义相同。
在上述反应式中,在化学式1的染料的制造中,作为起始物质使用的化学式2a、2b、2e、2f、2n和2r、以及化学式3的化合物可以通过通常的方法制造或购买而使用。
另外,本发明提供染料增感光电转换元件,上述染料增感光电转换元件的特征在于在氧化物半导体微粒上担载由上述化学式1表示的染料。本发明除了染料增感光电转换元件使用由上述化学式1表示的染料以外,还可以适用利用以往的染料制造太阳能电池用染料增感光电转换元件的制造方法,优选地,本发明的染料增感光电转换元件利用氧化物半导体微粒在基板上制造氧化物半导体的薄膜,接着,在上述薄膜上担载本发明的染料。
在本发明中,作为设置氧化物半导体的薄膜的基板,优选其表面具有导电性的基板,还可以使用市场上销售的基板。作为具体的例子,可以利用在玻璃的表面、或者聚对苯二甲酸乙二醇酯或聚醚砜等具有透明性的高分子材料的表面形成涂布有铟、氟、锑的氧化锡等导电性金属氧化物或钢、银、金等金属薄膜的基板。此时,导电性一般优选为1000Ω以下,特别优选100Ω为以下。
另外,作为氧化物半导体的微粒优选金属氧化物。作为具体的例子,可以优选使用钛、锡、锌、钨、锆、镓、铟、钇、铌、钽、钒等的氧化物。其中,优选钛、锡、锌、铌、铟等的氧化物,其中,更优选氧化钛、氧化锌、氧化锡,最优选氧化钛。上述氧化物半导体可以单独使用,也可以混合或涂布在半导体的表面而使用。
另外,上述氧化物半导体的微粒的粒径优选以平均粒径计为1~500nm,更优选为1~100nm。另外,该氧化物半导体的微粒还可以将大粒径的和小粒径的混合,或者形成多层来利用。
上述氧化物半导体薄膜可以通过以下方法制造:将氧化物半导体微粒用喷雾等直接在基板上形成薄膜的方法,将基板作为电极以电析出半导体微粒薄膜的方法,将半导体微粒的淤浆或含有能够通过水解半导体醇盐等半导体微粒的前体而得到的微粒的糊剂涂布在基板上后,通过干燥、固化或烧成的方法等,优选将糊剂涂布在基板上的方法。在该方法的情况下,淤浆可以通过采用通常的方法将二次凝集的氧化物半导体微粒进行分散而使其在分散介质中的平均一次粒径为1~200nm来得到。
作为分散淤浆的分散介质只要是能够分散半导体微粒的分散介质就能够没有特别的限制地使用,可以利用水、乙醇等醇、丙酮、乙酰丙酮等酮或己烷等烃,也可以将它们混合使用,其中,从减少淤浆的粘度变化的方面考虑,优选利用水。另外,以稳定氧化物半导体微粒的分散状态为目的,可以使用分散稳定剂。可以使用的分散稳定剂的具体例子可以举出醋酸、盐酸、硝酸等酸,或者乙酰丙酮、丙烯酸、聚乙二醇、聚乙烯醇等。
涂布有淤浆的基板可以进行烧成,其烧成温度为100℃以上,优选为200℃以上,另外上限大致为基材的熔点(软化点)以下,通常上限为900℃,优选为600℃以下。在本发明中,烧成时间没有特别的限定,但是优选大致为4小时以内。
在本发明中,基板上的薄膜的厚度为1~200μm比较合适,优选为1~50μm。进行烧成的情况下,虽然氧化物半导体微粒的薄层有一部分熔接,但是这样的熔接对本发明没有特别的影响。
另外,还可以对上述氧化物半导体薄膜实施二次处理。作为一个例子,还可以在与半导体相同的金属的醇盐、氯化物、氮化物、硫化物等的溶液中直接按照不同的基板沉积薄膜,并干燥或再烧成,从而提高半导体薄膜的性能。作为金属醇盐可以举出乙醇钛盐、异丙醇钛盐、叔丁醇钛盐、正二丁基二乙酰基锡等,可以利用它们的醇溶液。作为氯化物可以举出例如四氯化钛、四氯化锡、氯化锌等,可以利用其水溶液。这样获得的氧化物半导体薄膜由氧化物半导体微粒组成。
另外,在本发明中,在形成薄膜状的氧化物半导体微粒上担载染料的方法没有特别的限定,作为具体的例子可以举出以下方法:在将上述化学式1表示的染料用能够溶解其的溶剂进行溶解而得到的溶液或将染料进行分散而得到的分散液中浸渍设置有上述氧化物半导体薄膜的基板。溶液或分散液中的浓度可以根据染料适当地决定。浸渍温度大致为从常温至溶剂的沸点,另外,浸渍时间是1分钟至48小时左右。作为能够用于溶解染料的溶剂的具体例子可以举出甲醇、乙醇、乙腈、二甲基亚砜、二甲基甲酰胺、丙酮、叔丁醇等。溶液的染料浓度一般为1×10-6M~1M比较合适,优选为1×10-5M~1×10-1M。这样能够得到具有被染料增感的薄膜状的氧化物半导体微粒的本发明的光电转换元件。
在本发明中担载的由化学式1表示的染料可以为1种,也可以将数种混合。另外,在进行混合的情况下,本发明的染料可以同时与其他染料或金属配位化合物染料混合。能够进行混合的金属配位化合物染料的例子没有特别的限定,但是优选钌配位化合物或其季盐、酞菁、卟啉等,作为混合利用的有机染料可以举出无金属的酞菁、卟啉,或者花青苷,部花青,氧杂菁,三苯代甲烷系,WO2002/011213号公开的丙烯酸系染料等的次甲基系染料,或者呫吨系、偶氮系、蒽醌系、苝系等的染料(参照文献[M.K.Nazeeruddin,A.Kay,I.Rodicio,R.Humphry-Baker,E.Muller,P.Liska,N.Vlachopoulos,M.Gratzel,J.Am.Chem.Soc.,第115卷,6382侧(1993年)])。使用2种以上的染料的情况下,可以将染料依次吸附在半导体薄膜上,也可以混合溶解后吸附。
另外,在本发明中,在氧化物半导体微粒的薄膜上担载染料时,为了防止染料之间的结合,优选在包合物的存在下担载染料。作为上述包合物可以使用脱氧胆酸、脱氢脱氧胆酸、鹅脱氧胆酸、胆酸甲酯、胆酸钠等胆酸类,聚环氧乙烷、胆酸等的类固醇系化合物,冠醚,环糊精、杯芳烃、聚环氧乙烷等。
另外,担载染料后,可以用4-叔丁基吡啶等胺化合物或醋酸、丙酸等具有酸性基团的化合物等处理半导体电极表面。处理方法可以使用例如在胺的乙醇溶液中浸泡设置有担载了染料的半导体微粒薄膜的基板的方法等。
另外,本发明提供以包括上述染料敏化光电转换元件为特征的染料敏化太阳能电池,除了使用利用了担载有由上述化学式1表示的染料的氧化物半导体微粒的染料增感光电转换元件以外,理所当然地可以适用使用以往的光电转换元件制造太阳能电池的通常的方法,作为具体的例子,可以由在上述氧化物半导体微粒上担载了由化学式1表示的染料的光电转换元件电极(阴极)、对电极(阳极)、氧化还原电解质、空穴输送材料或p型半导体等构成。
优选地,作为本发明的染料敏化太阳能电池的具体的制造方法的一个例子,可以通过以下步骤制造:在导电性透明基板上涂布氧化钛糊剂的步骤;烧成涂布有糊剂的基板而形成氧化钛薄膜的步骤;将形成有氧化钛薄膜的基板浸渍在溶解有由化学式1表示的染料的混合溶液中,形成吸附有染料的氧化钛膜电极的步骤;在其上部设置形成有对电极的第二玻璃基板的步骤;形成贯通第二玻璃基板和对电极的孔(hole)的步骤;在上述对电极和吸附有上述染料的氧化钛膜电极之间设置热塑性高分子膜,并实施热压工序,从而使上述对电极和氧化钛膜电极接合的步骤;通过上述孔向上述对电极和氧化钛膜电极之间的热塑性高分子膜注入电解质的步骤;以及用上述热塑性高分子进行密封的步骤。
氧化还原电解质、空穴输送材料、p型半导体等的形态可以是液体、凝固体(凝胶及凝胶状)、固体等。液体状的可以分别举出将氧化还原电解质、熔融盐、空穴输送材料、p型半导体等分别溶于溶剂中的或者常温熔融盐等,凝固体(凝胶及凝胶状)的情况可以分别举出使它们含在聚合物基质或低分子胶凝剂等中的等。固体的可以使用氧化还原电解质、熔融盐、空穴输送材料、p型半导体等。
作为空穴输送材料可以使用利用了胺衍生物或聚乙炔、聚苯胺、聚噻吩等导电性高分子,三亚苯系化合物等的盘状液晶相的产品。另外,作为p型半导体可以使用CuI、CuSCN等。作为对电极优选使用具有导电性、对氧化还原电解质的还原反应起到催化作用的对电极。例如,可以使用在玻璃或者高分子膜上蒸镀了铂、碳、铑、钌等,或者涂布有导电性微粒的对电极。
作为用于本发明的太阳能电池的氧化还原电解质可以使用将卤素离子作为抗衡离子的卤素化合物和卤素分子所组成的卤素氧化还原系电解质,氰亚铁酸盐-氰亚铁酸盐或二茂铁-二茂铁离子、钴配位化合物等金属配位化合物等的金属氧化还原系电解质、烷基硫醇-烷基二硫化物、紫罗碱染料、氢醌-醌等有机氧化还原系电解质等,优选卤素氧化还原系电解质。作为由卤素化合物-卤素分子组成的卤素氧化还原系电解质中的卤素分子优选碘分子。另外,作为将卤素离子作为抗衡离子的卤素化合物可以使用LiI、NaI、KI、CaI2、MgI2、CuI等卤化金属盐,或者四烷基碘化铵、咪唑碘、吡啶碘等卤素的有机铵盐,或者I2。
另外,氧化还原电解质由包含它的溶液的形态存在时,该溶剂可以使用电化学上具有惰性的溶剂。作为具体例子可以举出乙腈、碳酸亚丙酯、碳酸亚乙酯、3-甲氧基丙腈、甲氧基乙腈、乙二醇、丙二醇、一缩二乙二醇、二缩三乙二醇、丁内酯、二甲氧基乙烷、碳酸二甲酯、1,3-二氧戊环、甲酸甲酯、2-甲基四氢呋喃、3-甲氧基-唑烷-2-酮、环丁砜、四氢呋喃、水等,特别优选乙腈、碳酸亚丙酯、碳酸亚乙酯、3-甲氧基丙腈、乙二醇、3-甲氧基-唑烷-2-酮、丁内酯等。上述溶剂可以使用1种或者混合使用。在凝胶状的阳电解质的情况下,可以使用在低聚物、聚合物等的基质中含有电解质或电解质溶液的两性电解质,或者在低分子胶凝剂等中同样含有电解质或电解质溶液的阳电解质。氧化还原电解质的浓度优选为0.01-99重量%,更优选0.1-30重量%。
本发明的太阳能电池可以通过以下方法得到,在基板上的氧化物半导体微粒上担载有染料的光电转换元件(阴极)上,与其对置地配置对电极(阳极),并在它们之间填充含有氧化还原电解质的溶液。
实施例
染料的合成
所有反应均在氩气氛围中进行,溶剂用从西格玛奥德里奇(Sigma-Adrich)公司购买的适当的试剂蒸馏。1H NMR谱是用Varian Mercury 300光谱仪测定。吸光和发光谱是分别用Perkin-Elmer Lambda 2S UV-visible光谱仪和Perkin LS荧光光谱仪测定。
实施例1化学式1a的化合物的合成
(1-1)将(2,3-二氢噻吩并[3,4-b][1,4]二噁英-5-基)三甲基锡烷(0.40g,1.34mmol)、化学式2a的化合物(0.75g,1.12mmol)、Pd(PPh3)4(0.065g,0.056mmol)溶于THF(40ml)后,在氮气氛围下回流8小时。接着,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-MC∶Hx=1∶4),从而合成了化学式4a的化合物。
1H NMR(CDCl3):[ppm]=0.96(m,6H),1.29(m,4H),1.96(m,4H),2.55(m,8H),2.62(m,4H),4.68(s,2H),4.71(s,2H),6.71(m,2H),6.96(s,1H),7.08(s,1H),7.18(m,4H),7.38(m,2H),7.45(m,6H),7.55(d,3JHH=8.8Hz,2H).
(1-2)将化学式4a的化合物(0.87g,1.2mmol)溶于DMF(20ml)后,在0℃下徐徐滴加POCl3(0.13ml 1.44mmol),在80℃下搅拌4小时。搅拌结束后,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-EA∶Hx=1∶2),从而合成了化学式5a的化合物。
1H NMR(CDCl3):[ppm]=0.96(m,6H),1.29(m,4H),1.96(m,4H),2.55(m,8H),2.62(m,4H),4.68(s,2H),4.71(s,2H),6.71(m,2H),7.08(s,1H),7.18(m,4H),7.38(m,2H),7.45(m,6H),7.53(d,3JHH=8.8Hz,2H),9.54(s,1H).
(1-3)将化学式5a的化合物(0.58g,0.77mmol)、氰基乙酸(0.08g,0.93mmol)、哌啶(0.92ml,0.93mmol)溶于乙腈(20ml)后,在氮气氛围下回流4小时。接着,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-EA∶EtOH=10∶1),从而合成了化学式1a的化合物。
1H NMR(DMSO):[ppm]=0.96(m,6H),1.29(m,4H),1.44(s,12H),1.96(m,4H),2.55(m,8H),2.62(m,4H),4.68(s,2H),4.71(s,2H),6.98(m,2H),7.08(s,1H),7.2(m,4H),7.39(m,2H),7.42(m,6H),7.53(d,3JHH=8.8Hz,2H),11.48(s,1H).
实施例2化学式1b的化合物的合成
(2-1)将(2,3-二氢噻吩并[3,4-b][1,4]二噁英-5-基)三甲基锡烷(0.40g,1.34mmol)、化学式2b的化合物(1g,1.12mmol)、Pd(PPh3)4(0.065g,0.056mmol)溶于THF(40ml)后,在氮气氛围下回流8小时。接着,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-MC∶Hx=1∶4),从而合成了化学式4b的化合物。
1H NMR(CDCl3):[ppm]=0.96(m,6H),1.29(m,4H),1.44(s,12H),1.96(m,4H),2.55(m,8H),2.62(m,4H),4.68(s,2H),4.71(s,2H),6.91(s,1H),6.96(s,1H),7.08(s,1H),7.18(m,6H),7.38(m,6H),7.55(m,4H),7.82(d,3JHH=8.8Hz,2H).
(2-2)将化学式4a的化合物(1.14g,1.2mmol)溶于DMF(20ml)后,在0℃下徐徐滴加POCl3(0.13ml1.44mmol),在80℃下搅拌4小时。搅拌结束后,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-EA∶Hx=1∶2),从而合成了化学式5b的化合物。
1H NMR(CDCl3):[ppm]=0.96(m,6H),1.29(m,4H),1.44(s,12H),1.96(m,4H),2.55(m,8H),2.62(m,4H),4.68(s,2H),4.71(s,2H),6.93(s,1H),7.08(s,1H),7.18(m,6H),7.38(m,6H),7.55(m,4H),7.82(d,3JHH=8.8Hz,2H),9.51(s,1H).
(2-3)将化学式5b的化合物(0.75g,0.77mmol)、氰基乙酸(0.08g,0.93mmol)、哌啶(0.92ml,0.93mmol)溶于乙腈(20ml)后,在氮气氛围下回流4小时。接着,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-EA∶EtOH=10∶1),从而合成了化学式1b的化合物。
1H NMR(DMSO):[ppm]=0.96(m,6H),1.29(m,4H),1.44(s,12H),1.96(m,4H),2.55(m,8H),2.62(m,4H),4.68(s,2H),4.71(s,2H),6.98(m,2H),7.08(s,1H),7.15(m,6H),7.32(m,6H),7.55(m,4H),7.80(d,3JHH=8.8Hz,2H),11.51(s,1H).
实施例3化学式1e的化合物的合成
(3-1)将(2,3-二氢噻吩并[3,4-b][1,4]二噁英-5-基)三甲基锡烷(0.40g,1.34mmol)、5-溴-2-(4-(2,2-二苯基乙烯基)苯基)-3-己基噻吩(化学式2e的化合物)(0.67g,1.34mmol)、Pd(PPh3)4(0.065g,0.056mmol)溶于THF(40ml)后,在氮气氛围下回流8小时。接着,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-MC∶Hx=1∶4),从而合成了化学式4e的化合物。
1H NMR(CDCl3):[ppm]=0.88(m,3H),1.29(m,2H),1.86(m,2H),2.55(m,4H),2.62(m,2H),4.68(s,2H),4.71(s,2H),6.71(s,1H),6.96(s,1H),7.08(s,1H),7.18(m,4H),7.38(m,2H),7.45(m,6H),7.55(d,3JHH=8.8Hz,2H).
(3-2)将化学式4e的化合物(1.14g,1.2mmol)溶于DMF(20ml)后,在0℃下徐徐滴加POCl3(0.13ml 1.44mmol),在80℃下搅拌4小时。搅拌结束后,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-EA∶Hx=1∶2),从而合成了化学式5e的化合物。
1H NMR(CDCl3):[ppm]=0.92(m,3H),1.31(m,2H),1.86(m,2H),2.58(m,4H),2.65(m,2H),4.68(s,2H),4.73(s,2H),6.71(s,1H),6.96(s,1H),7.18(m,4H),7.42(m,2H),7.48(m,6H),7.55(d,3JHH=8.8Hz,2H),9.56(s,1H).
(3-3)将化学式5e的化合物(0.75g,0.77mmol)、氰基乙酸(0.08g,0.93mmol)、哌啶(0.92ml,0.93mmol)溶于乙腈(20ml)后,在氮气氛围下回流4小时。接着,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-EA∶EtOH=10∶1),从而合成了化学式1e的化合物。
1H NMR(DMSO):[ppm]=0.96(m,3H),1.29(m,2H),1.96(m,2H),2.55(m,4H),2.62(m,2H),4.68(s,2H),4.71(s,2H),6.98(m,2H),7.08(s,1H),7.18(m,4H),7.42(m,2H),7.51(m,6H),7.58(d,3JHH=8.8Hz,2H),11.54(s,1H).
实施例4化学式1f的化合物的合成
(4-1)将(2,3-二氢噻吩并[3,4-b][1,4]二噁英-5-基)三甲基锡烷(0.40g,1.34mmol)、N-(4-(5-溴-3-己基噻吩-2-基)苯基)-N-(9,9-二甲基-9H-芴-2-基)-9,9-二甲基-9H-芴-2-胺(化学式2f的化合物)(0.97g,1.34mmol)、Pd(PPh3)4(0.065g,0.056mmol)溶于THF(40ml)后,在氮气氛围下回流8小时。接着,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-MC∶Hx=1∶4),从而合成了化学式4f的化合物。
1H NMR(CDCl3):[ppm]=0.89(m,3H),1.29(m,4H),1.47(s,12H),1.52(m,4H),2.52(m,2H),4.68(s,2H),4.71(s,2H),6.93(s,1H),6.98(s,1H),7.09(m,4H),7.31(m,4H),7.38(m,4H),7.58(d,3JHH=11.6Hz,2H),7.62.(m,4H).
(4-2)将化学式4f的化合物(1.14g,1.2mmol)溶于DMF(20ml)后,在0℃下徐徐滴加POCl3(0.13ml 1.44mmol),在80℃下搅拌4小时。搅拌结束后,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-EA∶Hx=1∶2),从而合成了化学式5f的化合物。
1H NMR(CDCl3):[ppm]=0.89(m,3H),1.29(m,4H),1.47(s,12H),1.52(m,4H),2.52(m,2H),4.68(s,2H),4.71(s,2H),6.93(s,1H),7.09(m,4H),7.31(m,4H),7.38(m,4H),7.58(d,3JHH=11.6Hz,2H),7.62.(m,4H),9.51(s,1H).
(4-3)将化学式5f的化合物(0.75g,0.77mmol)、氰基乙酸(0.08g,0.93mmol)、哌啶(0.92ml,0.93mmol)溶于乙腈(20ml)后,在氮气氛围下回流4小时。接着,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-EA∶EtOH=10∶1),从而合成了化学式1f的化合物。
1H NMR(DMSO):[ppm]=0.96(m,3H),1.29(m,2H),1.44(s,12H),1.96(m,2H),2.55(m,4H),2.62(m,2H),4.68(s,2H),4.71(s,2H),6.96(s,1H),7.08(s,1H),7.15(m,6H),7.32(m,6H),7.55(m,4H),7.80(d,3JHH=8.8Hz,2H),11.51(s,1H).
实施例5化学式1n的化合物的合成
(5-1)将(2,3-二氢噻吩并[3,4-b][1,4]二噁英-5-基)三甲基锡烷(0.81g,2.66mmol)、N-(4-溴苯基)-N-(9,9-二甲基-9H-芴-2-基)-9,9-二甲基-9H-芴-2-胺(化学式2n的化合物)(1.78g,3.2mmol)、Pd(PPh3)4(0.15g,0.13mmol)溶于甲苯(40ml)后,在氮气氛围下回流8小时。接着,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-MC∶Hx=1∶4),从而合成了化学式4n的化合物。
1H NMR(CDCl3):[ppm]=1.47(s,12H),4.68(s,2H),4.71(s,2H),6.98(s,1H),7.09(m,4H),7.31(m,4H),7.38(m,4H),7.58(d,3JHH=11.6Hz,2H),7.62.(m,4H).
(5-2)将化学式4n的化合物(N-(4-(2,3-二氢噻吩并[3,4-b][1,4]二噁英-5-基)-N-(9,9-二甲基-9H-芴-2-基)-9,9-二甲基-9H-芴-2-胺)(1.84g,2.98mmol)、N-溴代苯乙烯(0.64g,3.57mmol)溶于30ml THF中后,在氮气氛围下搅拌。接着,将用二氯甲烷和水萃取有机层后蒸馏而得到的N-(4-(7-溴-2,3-二氢噻吩并[3,4-b][1,4]二噁英-5-基)-N-(9,9-二甲基-9H-芴-2-基)-9,9-二甲基-9H-芴-2-胺)(化学式7n的化合物)(1.95g,2.8mmol)、3’,4-二己基-2,2’-双噻吩-5-基硼酸(0.88g,2.33mmol)、K2CO3(0.64g,4.66mmol)、Pd(PPh3)4(0.13g,0.12mmol)溶于DMF(40ml)后,在氮气氛围下回流8小时。接着,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-MC∶Hx=1∶4),从而合成了化学式9n的化合物。
1H NMR(CDCl3):[ppm]=0.98(m,6H),1.28(m,4H),1.44(s,12H),1.96(m,4H),2.55(m,8H),2.62(m,4H),4.64(s,2H),4.70(s,2H),6.92(s,1H),6.96(s,1H),7.10(s,1H),7.18(m,6H),7.38(m,6H),7.56(m,4H),7.84(d,3JHH=8.8Hz,2H).
(5-3)将化学式9n的化合物(N-(4-(7-(3’,4-二己基-2,2’-双噻吩-5-基)-2,3-二氢噻吩并[3,4-b][1,4]二噁英-5-基)苯基)-N-(9,9-二甲基-9H-芴-2-基)-9,9-二甲基-9H-芴-2-胺)(1.06g,1.12mmol)溶于DMF(20ml)后,在0℃下徐徐滴加POCl3(0.13ml 1.44mmol),在80℃下搅拌4小时。搅拌结束后,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-EA∶Hx=1∶2),从而合成了化学式10n的化合物。
1H NMR(CDCl3):[ppm]=0.96(m,6H),1.29(m,4H),1.44(s,12H),1.96(m,4H),2.55(m,8H),2.62(m,4H),4.68(s,2H),4.71(s,2H),6.93(s,1H),7.08(s,1H),7.18(m,6H),7.38(m,6H),7.55(m,4H),7.82(d,3JHH=8.8Hz,2H),9.54(s,1H).
(5-4)将化学式10n的化合物(5’-(7-(4-双(9,9-二甲基-9H-芴-2-基)氨基)苯基)-2,3-二氢噻吩并[3,4-b][1,4]二噁英-5-基)-3,4’-二己基-2,2’-双噻吩-5-羧醛)(0.75g,0.77mmol)、氰基乙酸(0.08g,0.93mmol)、哌啶(0.92ml,0.93mmol)溶于乙腈(20ml)后,在氮气氛围下回流4小时。接着,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-EA∶EtOH=10∶1),从而合成了化学式1n的化合物。
1H NMR(DMSO):[ppm]=0.94(m,6H),1.28(m,4H),1.42(s,12H),1.98(m,4H),2.56(m,8H),2.62(m,4H),4.68(s,2H),4.74(s,2H),6.98(m,2H),7.11(s,1H),7.20(m,6H),7.34(m,6H),7.56(m,4H),7.82(d,3JHH=8.8Hz,2H),11.54(s,1H).
实施例6化学式1r的化合物的合成
(6-1)将(2,3-二氢噻吩并[3,4-b][1,4]二噁英-5-基)三甲基锡烷(0.81g,2.66mmol)、1-溴4-(2,2-二苯基乙烯基)苯基(化学式2r的化合物)(1.7g,3.2mmol)、Pd(PPh3)4(0.15g,0.13mmol)溶于甲苯(40ml)后,在氮气氛围下回流8小时。接着,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-MC∶Hx=1∶4),从而合成了化学式4r的化合物。
1H NMR(CDCl3):[ppm]=4.68(s,2H),4.72(s,2H),6.71(s,1H),6.96(s,1H),7.08(s,1H),7.18(m,4H),7.40(m,2H),7.48(m,6H),7.56(d,3JHH=8.8Hz,2H).
(6-2)将化学式4r的化合物(5-(4-(2,2-二苯基乙烯基)苯基-2,3-二氢噻吩并[3,4-b][1,4]二噁英)(1.18g,3.00mmol)、N-溴代苯乙烯(0.64g,3.57mmol)溶于30ml THF中后,在氮气氛围下搅拌。接着,将用二氯甲烷和水萃取有机层后蒸馏而得到的5-溴-7-(4-(2,2-二苯基乙烯基)苯基)-2,3-二氢噻吩并[3,4-b][1,4]二噁英(化学式7r的化合物)(1.33g,2.8mmol)、3’,4-二己基-2,2’-双噻吩-5-基硼酸(0.88g,2.33mmol)、K2CO3(0.64g,4.66mmol)、Pd(PPh3)4(0.13g,0.12mmol)溶于DMF(40ml)后,在氮气氛围下回流8小时。接着,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-MC∶Hx=1∶4),从而合成了化学式9r的化合物。
1H NMR(CDCl3):[ppm]=0.96(m,6H),1.29(m,4H),1.96(m,4H),2.55(m,8H),2.62(m,4H),4.68(s,2H),4.71(s,2H),6.71(m,2H),6.96(s,1H),7.08(s,1H),7.18(m,4H),7.38(m,2H),7.45(m,6H),7.55(d,3JHH=8.8Hz,2H).
(6-3)将化学式9r的化合物(5-(3’,4-二己基-2,2’-双噻吩-5-基)-7-(4-(2,2-二苯基乙烯基)苯基)-2,3-二氢噻吩并[3,4-b][1,4]二噁英)(0.87g,1.2mmol)溶于DMF(20ml)后,在0℃下徐徐滴加POCl3(0.13ml 1.44mmol),在80℃下搅拌4小时。搅拌结束后,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-EA∶Hx=1∶2),从而合成了化学式10r的化合物。
1H NMR(CDCl3):[ppm]=0.96(m,6H),1.29(m,4H),1.96(m,4H),2.55(m,8H),2.62(m,4H),4.68(s,2H),4.71(s,2H),6.72(m,2H),7.10(s,1H),7.18(m,4H),7.38(m,2H),7.45(m,6H),7.54(d,3JHH=8.8Hz,2H),9.54(s,1H).
(6-4)将化学式10r的化合物(5-(7-(4-(2,2-二苯基乙烯基)苯基)-2,3-二氢噻吩并[3,4-b][1,4]二噁英-5-基)-3’,4-二己基-2,2’-双噻吩-5-羧醛)(0.58g,0.77mmol)、氰基乙酸(0.08g,0.93mmol)、哌啶(0.92ml,0.93mmol)溶于乙腈(20ml)后,在氮气氛围下回流4小时。接着,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-EA∶EtOH=10∶1),从而合成了化学式1r的化合物。
1H NMR(DMSO):[ppm]=0.96(m,6H),1.29(m,4H),1.44(s,12H),1.96(m,4H),2.55(m,8H),2.62(m,4H),4.68(s,2H),4.71(s,2H),6.98(m,2H),7.08(s,1H),7.2(m,4H),7.39(m,2H),7.42(m,6H),7.53(d,3JHH=8.8Hz,2H),11.48(s,1H).
实施例7化学式1q的化合物的合成
(7-1)将上述实施例6的(6-2)中得到的化学式7r的化合物(1.2g,2.52mmol)、3-己基噻吩-2-基硼酸(0.44g,2.1mmol)、K2CO3(0.58g,4.2mmol)、Pd(PPh3)4(0.12g,0.105mmol)溶于DMF(30ml)后,在氮气氛围下回流8小时。接着,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-MC∶Hx=1∶4),从而合成了化学式9r’的化合物。
1H NMR(CDCl3):[ppm]=0.88(m,3H),1.29(m,2H),1.86(m,2H),2.55(m,4H),2.62(m,2H),4.64(s,2H),4.70(s,2H),6.72(s,1H),6.96(s,1H),7.08(s,1H),7.18(m,4H),7.38(m,2H),7.44(m,6H),7.54(d,3JHH=8.8Hz,2H).
(7-2)将化学式9r’的化合物((5-(4-(2,2-二苯基乙烯基)苯基)-7-(3-己基噻吩-2-基)-2,3-二氢噻吩并[3,4-b][1,4]二噁英)(0.98g,1.2mmol)溶于DMF(20ml)后,在0℃下徐徐滴加POCl3(0.13ml 1.44mmol),在80℃下搅拌4小时。搅拌结束后,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-EA∶Hx=1∶2),从而合成了化学式10r’的化合物。
1H NMR(CDCl3):[ppm]=0.88(m,3H),1.30(m,2H),1.86(m,2H),2.58(m,4H),2.65(m,2H),4.68(s,2H),4.73(s,2H),6.71(s,1H),6.96(s,1H),7.18(m,4H),7.42(m,2H),7.50(m,6H),7.56(d,3JHH=8.8Hz,2H),9.58(s,1H).
(7-3)将化学式10r’的化合物(5-(7-(4-(2,2-二苯基乙烯基)苯基)-2,3-二氢噻吩并[3,4-b][1,4]二噁英-5-基)-4-己基噻吩-2-羧醛)(0.75g,0.77mmol)、氰基乙酸(0.08g,0.93mmol)、哌啶(0.92ml,0.93mmol)溶于乙腈(20ml)后,在氮气氛围下回流4小时。接着,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-EA∶EtOH=10∶1),从而合成了化学式1q的化合物。
1H NMR(DMSO):[ppm]=0.94(m,3H),1.29(m,2H),1.95(m,2H),2.56(m,4H),2.64(m,2H),4.68(s,2H),4.72(s,2H),6.98(m,2H),7.11(s,1H),7.20(m,4H),7.42(m,2H),7.51(m,6H),7.58(d,3JHH=8.8Hz,2H),11.54(s,1H).
实施例8化学式1m的化合物的合成
(8-1)将上述实施例5的(5-2)中得到的化学式7n的化合物(1.92g,1.34mmol)、3-己基噻吩-2-基硼酸(0.28g,1.34mmol)、K2CO3(0.64g,4.66mmol)、Pd(PPh3)4(0.13g,0.12mmol)溶于DMF(40ml)后,在氮气氛围下回流8小时。接着,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-MC∶Hx=1∶4),从而合成了化学式9n’的化合物。
1H NMR(CDCl3):[ppm]=0.89(m,3H),1.29(m,4H),1.47(s,12H),1.52(m,4H),2.52(m,2H),4.68(s,2H),4.71(s,2H),6.93(s,1H),6.98(s,1H),7.09(m,4H),7.31(m,4H),7.38(m,4H),7.58(d,3JHH=11.6Hz,2H),7.62.(m,4H).
(8-2)将化学式9n’的化合物(N-(9,9-二甲基-9H-芴-2-基)-N-(4-(7-(3-己基噻吩-2-基)-2,3-二氢噻吩并[3,4-b][1,4]二噁英-5-基)苯基)-9,9-二甲基-9H-芴-2-胺)(0.88g,1.12mmol)溶于DMF(20ml)后,在0℃下徐徐滴加POCl3(0.13ml1.44mmol),在80℃下搅拌4小时。搅拌结束后,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-EA∶Hx=1∶2),从而合成了化学式10n’的化合物。
1H NMR(CDCl3):[ppm]=0.89(m,3H),1.29(m,4H),1.47(s,12H),1.52(m,4H),2.52(m,2H),4.68(s,2H),4.74(s,2H),6.94(s,1H),7.12(m,4H),7.32(m,4H),7.40(m,4H),7.56(d,3JHH=11.6Hz,2H),7.62.(m,4H),9.54(s,1H).
(8-3)将化学式10n’的化合物(5-(7-(4-双(9,9-二甲基-9H-芴-2-基)氨基)苯基)-2,3-二氢噻吩并[3,4-b][1,4]二噁英-5-基)-4-己基噻吩-5-羧醛)(0.75g,0.77mmol)、氰基乙酸(0.08g,0.93mmol)、哌啶(0.92ml,0.93mmol)溶于乙腈(20ml)后,在氮气氛围下回流4小时。接着,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-EA∶EtOH=10∶1),从而合成了化学式1n的化合物。
1H NMR(DMSO):[ppm]=0.96(m,3H),1.29(m,2H),1.44(s,12H),1.96(m,2H),2.55(m,4H),2.62(m,2H),4.68(s,2H),4.71(s,2H),6.98(s,1H),7.11(s,1H),7.20(m,6H),7.42(m,6H),7.58(m,4H),7.80(d,3JHH=8.8Hz,2H),11.52(s,1H).
实施例9化学式1w的化合物的合成
(9-1)将上述实施例3的(3-1)中得到的化学式4e的化合物(5-(5-(4-(2,2-二苯基乙烯基)苯基)-4-己基噻吩-2-基)-2,3-二氢噻吩并[3,4-b][1,4]二噁英))(1.2g,2.13mmol)和N-溴代苯乙烯(0.45g,2.56mmol)溶于30ml THF后,在氮气氛围下搅拌4小时。接着,将用二氯甲烷和水萃取有机层后蒸馏而得到的5-溴-7-(5-(4-(2,2-二苯基乙烯基)苯基)-4-己基噻吩-2-基)-2,3-二氢噻吩并[3,4-b][1,4]二噁英(化学式7w的化合物)(1.15g,1.8mmol)、3-己基噻吩-2-基硼酸(0.32g,1.5mmol)、K2CO3(0.42g,3mmol)、Pd(PPh3)4(0.086g,0.075mmol)溶于DMF(30ml)后,在氮气氛围下回流8小时。接着,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-MC∶Hx=1∶4),从而合成了化学式9w的化合物。
1H NMR(CDCl3):[ppm]=0.94(m,6H),1.28(m,4H),1.44(s,12H),1.98(m,4H),2.55(m,8H),2.64(m,4H),4.64(s,2H),4.72(s,2H),6.72(m,2H),6.98(s,1H),7.10(s,1H),7.20(m,4H),7.40(m,2H),7.48(m,6H),7.55(d,3JHH=8.8Hz,2H).
(9-2)将化学式9w的化合物(5-(5-(4-(2,2-二苯基乙烯基)苯基)-4-己基噻吩-2-基)-7-(3-己基噻吩-2-基)-2,3-二氢噻吩并[3,4-b][1,4]二噁英)(1.14g,1.2mmol)溶于DMF(15ml)后,在0℃下徐徐滴加POCl3(0.13ml 1.44mmol),在80℃下搅拌4小时。搅拌结束后,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-EA∶Hx=1∶2),从而合成了化学式10w的化合物。
1H NMR(CDCl3):[ppm]=0.94(m,6H),1.29(m,4H),1.44(s,12H),1.98(m,4H),2.55(m,8H),2.64(m,4H),4.64(s,2H),4.72(s,2H),6.71(m,2H),7.18(m,5H),7.38(m,2H),7.45(m,6H),7.53(d,3JHH=8.8Hz,2H),9.54(s,1H).
(9-3)将化学式10w的化合物(5-(7-(5-(4-(2,2-二苯基乙烯基)苯基)-4-己基噻吩-2-基)-2,3-二氢噻吩并[3,4-b][1,4]二噁英-5-基)-4-己基噻吩-2-羧醛)(1.05g,0.8mmol)、氰基乙酸(0.08g,0.93mmol)、哌啶(0.92ml,0.93mmol)溶于乙腈(20ml)后,在氮气氛围下回流4小时。接着,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-EA∶EtOH=10∶1),从而合成了化学式1w的化合物。
1H NMR(DMSO):[ppm]=0.96(m,6H),1.29(m,4H),1.44(s,12H),1.96(m,4H),2.55(m,8H),2.62(m,4H),4.68(s,2H),4.71(s,2H),6.98(m,2H),7.06(s,1H),7.20(m,6H),7.36(m,6H),7.52(m,4H),7.84(d,3JHH=8.8Hz,2H),11.50(s,1H).
实施例10化学式1u的化合物的合成
(10-1)将上述实施例4的(4-1)中得到的化学式4f的化合物(N-(4-(5-(2,3-二氢噻吩并[3,4-b][1,4]二噁英-5-基)-3-己基噻吩-2-基)苯基-N-(9,9-二甲基-9H-芴-2-基)-9,9-二甲基-9H-芴-2-胺)(1.64g,2.10mmol)和N-溴代苯乙烯(0.44g,2.54mmol)溶于30ml THF后,在氮气氛围下搅拌4小时。接着,将用二氯甲烷和水萃取有机层后蒸馏而得到的N-(4-(5-(7-溴-2,3-二氢噻吩并[3,4-b][1,4]二噁英-5-基)-3-己基噻吩-2-基)苯基-N-(9,9-二甲基-9H-芴-2-基)-9,9-二甲基-9H-芴-2-胺(化学式7u的化合物)(1.53g,1.78mmol)、3-己基噻吩-2-基硼酸(0.32g,1.5mmol)、K2CO3(0.42g,3mmol)、Pd(PPh3)4(0.086g,0.075mmol)溶于DMF(30ml)后,在氮气氛围下回流8小时。接着,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-MC∶Hx=1∶4),从而合成了化学式9u的化合物。
1H NMR(CDCl3):[ppm]=0.94(m,6H),1.28(m,4H),1.44(s,12H),1.96(m,4H),2.55(m,8H),2.62(m,4H),4.68(s,2H),4.71(s,2H),6.90(s,1H),6.98(s,1H),7.10(s,1H),7.20(m,6H),7.40(m,6H),7.56(m,4H),7.84(d,3JHH=8.8Hz,2H).
(10-2)将化学式9u的化合物(N-(9,9-二甲基-9H-芴-2-基)-N-(4-(3-己基-5-(7-(3-己基噻吩-2-基)-2,3-二氢噻吩并[3,4-b][1,4]二噁英-5-基)噻吩-2-基)苯基-9,9-二甲基-9H-芴-2-胺)(1.14g,1.2mmol)溶于DMF(20ml)后,在0℃下徐徐滴加POCl3(0.13ml 1.44mmol),在80℃下搅拌4小时。搅拌结束后,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-EA∶Hx=1∶2),从而合成了化学式10u的化合物。
1H NMR(CDCl3):[ppm]=0.96(m,6H),1.29(m,4H),1.44(s,12H),1.96(m,4H),2.55(m,8H),2.62(m,4H),4.68(s,2H),4.71(s,2H),6.93(s,1H),7.08(s,1H),7.18(m,6H),7.38(m,6H),7.55(m,4H),7.82(d,3JHH=8.8Hz,2H),9.51(s,1H).
(10-3)将化学式10u的化合物(5-(7-(5-(4-双(9,9-二甲基-9H-芴-2-基)氨基)苯基)-4-己基噻吩-2-基)-2,3-二氢噻吩并[3,4-b][1,4]二噁英-5-基)-4-己基噻吩-2-羧醛)(0.75g,0.77mmol)、氰基乙酸(0.08g,0.93mmol)、哌啶(0.92ml,0.93mmol)溶于乙腈(20ml)后,在氮气氛围下回流4小时。接着,用二氯甲烷和水萃取有机层后,蒸馏,经柱色谱(洗脱液-EA∶EtOH=10∶1),从而合成了化学式1u的化合物。
1H NMR(DMSO):[ppm]=0.96(m,6H),1.29(m,4H),1.44(s,12H),1.96(m,4H),2.55(m,8H),2.62(m,4H),4.68(s,2H),4.71(s,2H),6.98(s,2H),7.08(s,1H),7.15(m,6H),7.32(m,6H),7.55(m,4H),7.80(d,3JHH=8.8Hz,2H),11.51(s,1H).
实施例11染料敏化太阳能电池的制造及物性测定
为了评价染料化合物的电流-电压特性,利用7或8μm TiO2透明层制造太阳能电池。将TiO2糊剂(Solaronix,13nm糊剂)进行丝网印刷来制造7或8μm厚度的TiO2透明层。用40mM TiCl4溶液处理该TiO2膜,在500℃中干燥30分钟。将处理后的膜冷却至60℃后,浸渍在上述实施例1至4制造的本发明的染料化合物1a、1b、1e和1f各自的溶液(10mM的含鹅脱氧胆酸的二氯甲烷和乙醇的混合物(MC∶EtOH=1∶1)中含0.3mM染料)中(化合物1a和1b为7μm厚度的TiO2透明层,化合物1e和1f为8μm厚度的TiO2透明层)。在吸附有染料的TiO2电极和铂-对电极之间放置作为隔片的高温熔融膜(Surlyn 1702,25μm厚度),进行加热,从而装配了密封的夹层结构电池。作为电解质溶液,使用了在乙腈中溶解了0.6M 3-己基-1,2-二甲基咪唑碘、0.04M I2、0.025M LiI和0.28M叔丁基吡啶的溶液。
测定分别使用本发明的染料化合物1a、1b、1e和1f制造的太阳能电池光电化学特性(photoelectrochemical characteristics),并表示在表1中。太阳能电池的光电化学特性是利用Keithley M236源测定装置进行测定,作为光源利用的是具有AM 1.5滤光片(Oriel)的300W Xe灯,电极大小为0.4×0.4cm2,光的强度为1sun(100mW/cm2)。光的强度是利用Si太阳能电池进行调整。
表1
在上述表1中,Jsc表示短路光电流密度(short-circuit photocurrent density)、Voc表示开路光电压(open circuit photovoltage)、FF表示填充因子(fill factor)。
产业上的利用可能性
本发明的染料化合物用于染料敏化太阳能电池(DSSC)时显示出比以往的染料更高的摩尔吸光系数、Jsc(短路光电流密度)和光电转换效率,可以大大提高太阳能电池的效率,即使不使用昂贵的柱也能够进行精制,从而可以突破性地降低染料合成成本。
Claims (10)
4.一种有机染料的制造方法,该有机染料由下述化学式1-2表示,该方法包括:
(i)使下述化学式2的化合物与下述化学式3的化合物进行铃木偶联反应来制造下述化学式4的化合物;
(ii)使化学式4的化合物在有机溶剂中与N-溴苯乙烯反应来制造下述化学式7的化合物;
(iii)使化学式7的化合物与下述化学式8的化合物进行铃木偶联反应来制造下述化学式9的化合物;
(iv)使化学式9的化合物在有机溶剂中与POCl3反应来制造下述化学式10的化合物;
(v)在CH3CN中,在哌啶存在下,使化学式10的化合物与氰基乙酸或下述化学式6的化合物反应,
化学式1-2
化学式2
化学式3
化学式4
化学式7
化学式8
化学式9
化学式10
化学式6
在上述式中,X、Y、R1至R5、Ar、Z、Z’、m和n与权利要求1中的定义相同,a为1至5的整数。
5.一种染料增感光电转换元件,其特征在于,包括担载有权利要求1所述的有机染料的氧化物半导体微粒。
6.根据权利要求5所述的染料增感光电转换元件,其特征在于,在包合物存在下,在所述氧化物半导体微粒上担载有机染料。
7.根据权利要求5所述的染料增感光电转换元件,其特征在于,所述氧化物半导体微粒含有作为必须成分的二氧化钛。
8.根据权利要求5所述的染料增感光电转换元件,其特征在于,所述氧化物半导体微粒的平均粒径为1~500nm。
9.一种染料敏化太阳能电池,其特征在于,包括作为电极的权利要求5所述的染料增感光电转换元件。
10.根据权利要求9所述的染料敏化太阳能电池,其特征在于,所述染料敏化太阳能电池通过以下步骤制造:在导电性透明基板上涂布氧化钛糊剂的步骤;烧成涂布有糊剂的基板而形成氧化钛薄膜的步骤;将形成有氧化钛薄膜的基板浸渍在溶解有由化学式1表示的染料的混合溶液中,形成吸附有染料的氧化钛膜电极的步骤;在其上部设置形成有对电极的第二玻璃基板的步骤;形成贯通第二玻璃基板和对电极的孔的步骤;在所述对电极和吸附有所述染料的氧化钛膜电极之间设置热塑性高分子膜,并实施热压工序,从而使所述对电极和氧化钛膜电极接合的步骤;通过所述孔向所述对电极和氧化钛膜电极之间的热塑性高分子膜注入电解质的步骤;以及用所述热塑性高分子进行密封的步骤。
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CN104254576A (zh) * | 2012-03-30 | 2014-12-31 | 巴斯夫欧洲公司 | 用于染料敏化太阳能电池的具有氟化抗衡阴离子的喹啉*染料 |
CN104487522A (zh) * | 2012-04-23 | 2015-04-01 | 艾尼股份公司 | 用于染料敏化太阳能电池的有机染料 |
CN105814707A (zh) * | 2013-11-15 | 2016-07-27 | 艾尼股份公司 | 用于染料敏化太阳能电池的有机染料 |
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