CN102245710A - 含有苯并噻二唑发色团的新型有机染料及其制造方法 - Google Patents
含有苯并噻二唑发色团的新型有机染料及其制造方法 Download PDFInfo
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- CN102245710A CN102245710A CN2009801473160A CN200980147316A CN102245710A CN 102245710 A CN102245710 A CN 102245710A CN 2009801473160 A CN2009801473160 A CN 2009801473160A CN 200980147316 A CN200980147316 A CN 200980147316A CN 102245710 A CN102245710 A CN 102245710A
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- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 title abstract 2
- 239000005964 Acibenzolar-S-methyl Substances 0.000 title abstract 2
- 238000002360 preparation method Methods 0.000 title 1
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- 238000006243 chemical reaction Methods 0.000 claims description 39
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 30
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
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Images
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
-
- 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
-
- 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
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
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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
-
- 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
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
-
- 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
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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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
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- 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
- H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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Abstract
本发明涉及一种含有苯并噻二唑发色团的新型有机染料及其制造方法,本发明的染料化合物具有比以往的染料更高的光电池性能和优异的稳定性,从而用于染料敏化太阳能电池(dye-sensitized solar cell,DSSC),能够大幅度提高电池的效率。
Description
技术领域
本发明涉及一种具有高的光电池性能和优异的稳定性、用于染料敏化太阳能电池(dye-sensitized solar cell,DSSC)的含有苯并噻二唑发色团的新型有机染料及其制造方法。
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(MichaelGratzel)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而广泛使用的是显示出10%以上的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并难以精制的缺点。
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-键体系连接。
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在可见光蓝色区域具有具有陡而窄的吸收带,从而导致光捕获能力的减少,具有热稳定性和光稳定性比较低的缺点。
因此,为了开发具有高的光电池性能和提高了的稳定性的有机染料而努力的结果,公开了在有机骨架内含有非平面性的双-二甲基芴氨基残基和双噻吩或三噻吩单元的有机染料,根据报告,该染料在使用没有溶剂的离子性液体电解质时,表现出7%的显著高的光电转换效率。另外,报告了进一步在交联性骨架上引入苯并噻二唑之类的低带隙发色团,从而进一步提高上述体系的光电池性能,在红色区域能够表现出提高了的光谱反应。
但是,在这种情况下,虽然在没有溶剂的条件下使用离子性液体电解质能够达到高的光电转换效率,但由于泄漏等导致仍然不能满足长期稳定性,因此,一直在努力开发具有高光电转换效率、且长期稳定性优异的有机染料。
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金属配位化合物染料和有机染料具有更高的光电池性能和优异的稳定性,从而能够大幅度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显著提高了的光电转换效率、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、以及效率显著提高了的太阳能电池。
技术方案
为了达到上述目的,本发明提供一种由下述化学式1~3中任一结构表示的噻吩系染料:
[化学式1]
[化学式2]
[化学式3]
在上述式中
R1为
上述X、Y和Z各自独立地为氢或C1-30的烷基、烷氧基或异烷氧基;
R2、R3、R4和R5各自独立地为氢、卤素、酰胺基、氰基、羟基、硝基、酰基、C1-30的烷基、C1-30的烷氧基、C1-30的烷基羰基或C6-20的芳基,为C1-30的烷氧基时,R2和R3、或R4和R5相互键合而形成含氧杂环;
Ar为被C1-50的烷基、烷氧基、卤素、酰胺基、氰基、羟基、硝基、酰基、芳基或杂芳基取代的或者非取代的C1-50的烷基、芳基、烷氧基或杂芳基;
n为1至10的整数。
另外,本发明提供由化学式1a或1b表示的染料的制造方法,包括:
(1)使下述化学式8的化合物与锡烷基噻吩或2-(3-己基噻吩-2-基)-4,4,5,5-四甲基[1,3,2]二氧杂硼烷进行斯泰尔(Stille)或铃木(Suzuki)偶联反应,制造下述化学式9a或9b的化合物,
(2)在有机溶剂中,使化学式9a或9b的化合物与N-溴代琥珀酰亚胺反应而进行溴化,制造下述化学式4a或4b的化合物,
(3)使化学式4a或4b的化合物与下述化学式5的化合物进行铃木偶联反应,制造下述化学式6a或6b的化合物,
(4)通过维尔斯迈尔-哈克(Vilsmeier-Haack)反应使化学式6a或6b的化合物进行醛化,制造下述化学式7a或7b的化合物,
(5)在氯仿中,在哌啶存在下,使化学式7a或7b的化合物与氰基乙酸反应。
[化学式8]
[化学式9a]
(R=H)
[化学式9b]
(R=己基)
[化学式4a]
(R=H)
[化学式4b]
(R=己基)
[化学式5]
[化学式6a]
(R=H)
[化学式6b]
(R=己基)
[化学式7a]
(R=H)
[化学式7b]
(R=己基)
[化学式1a]
(R=H)
[化学式1b]
(R=己基)
另外,本发明提供一种染料增感光电转换元件,其特征在于,含有担载有由上述化学式1~3中任一结构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
本发明的新型噻吩系染料相比于以往的金属配位化合物染料和有机染料显示更高的光电池性能,即更高的摩尔吸光系数、Jsc(短路光电流密度)和光电转换效率,并具有优异的稳定性,从而能够大幅度提高太阳能电池的效率。
附图说明
图1是实施例1和2中制造的染料JK-68和JK-69各自的在四氢呋喃(THF)中测定的吸光和发光光谱;
图2是对实施例1和2中制造的染料JK-68和JK-69各自以对B3LYP/3-21G的TD-DFT计算的最佳结构模式图;
图3是将对实施例1和2中制造的染料JK-68和JK-69各自利用B3LYP/3-21G而计算的几何形态以HOMO和LUMO的等密度(isodensity)表面图表示的图;
图4是实施例3中制造的DSSC的光电池性能(单色入射光子-对-电流转换效率(IPCEs)的谱图)及光电流密度-电压(J-V)曲线;
图5是将实施例3中制造的DSSC在加速化的老化条件下维持1000小时,并随着时间的推移而测定的短路光电流密度(JSC)、开路电压(VOC)、填充因子(fillfactor)和光电转换效率图;
图6是实施例3中制造的DSSC(为了进行比较,制造含有以往的染料JK-2的染料敏化太阳能电池来进行比较)的电子放出系数(a)和寿命(b)测定结果;
图7是将实施例3中制造的DSSC(为了进行比较,制造含有以往的染料JK-2的染料敏化太阳能电池来进行比较)的电化学阻抗(impedance)谱在明条件(a)和暗条件(b)下测定的结果。
具体实施方式
本发明的发明人们确认,将具有含苯并噻二唑发色团的新型有机染料结构的由化学式1~3表示的噻吩系染料化合物担载于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、稳定性优异,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。
本发明的有机染料的特征在于,由下述化学式1~3中任一结构表示。
[化学式1]
[化学式2]
[化学式3]
在上述式中,
R1、R2、R3、R4、R5、Ar和n与上述定义相同,优选上述R1为
R2、R3、R4和R5各自独立地为氢或C4-10的烷基,Ar为
(*:键合部),n为1。
另外,代表性地,如下述反应式1所示,根据本发明的由化学式1a或1b表示的染料通过以下方法制造:
(1)使下述化学式8的化合物与三丁基(2-噻吩基)锡烷 或2-(3-己基噻吩-2-基)-4,4,5,5-四甲基[1,3,2]二氧杂硼烷进行斯泰尔(Stille)或铃木(Suzuki)偶联反应,制造下述化学式9a或9b的化合物,
(2)在有机溶剂(例如乙酸和二氯甲烷的混合物)中,使化学式9a或9b的化合物与N-溴代琥珀酰亚胺反应而进行溴化,制造下述化学式4a或4b的化合物,
(3)使化学式4a或4b的化合物与下述化学式5的化合物进行铃木偶联反应,制造下述化学式6a或6b的化合物,
(4)通过维尔斯迈尔-哈克(Vilsmeier-Haack)反应使化学式6a或6b的化合物进行醛化,制造下述化学式7a或7b的化合物,
(5)在氯仿中,在哌啶存在下,使化学式7a或7b的化合物与氰基乙酸反应。
[反应式1]
在化学式1a或1b的染料的制造中作为起始物质使用的化学式8的化合物可以采用通常的方法来制造。
另外,本发明提供一种染料增感光电转换元件,所述染料增感光电转化元件的特征在于,氧化物半导体微粒上担载有由上述化学式1、化学式2或化学式3表示的染料。本发明的染料增感光电转换元件除了使用由上述化学式1、化学式2或化学式3表示的染料以外,当然可以适用利用以往染料制造太阳能电池用染料增感光电转换元件的方法,优选地,本发明的染料增感光电转换元件适合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,特别优选为100Ω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来制造,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2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1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可以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2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:在将由上述化学式1、化学式2或化学式3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。沉积时间大致为从常温至溶剂的沸点,另外,沉积时间是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、化学式2或化学式3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进行混合。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、化学式2或化学式3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、化学式2或化学式3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上述溶解有由化学式1、化学式2或化学式3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2玻璃基板的步骤;形成贯通第2玻璃基板和对电极的孔(hole)的步骤;在上述对电极和上述吸附有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阳电解质,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。
以下,为了助于理解本发明,提供优选实施方式,但下述实施方式仅例示本发明,本发明的范围并不限定于下述实施方式。
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。吸光和发光光谱是分别用Perkin-Elmer Lambda 2S UV-visible光谱仪和PerkinLS荧光光谱仪测定。
实施例1化合物1a(JK-68)的合成
[化学式1a]
(1-1)4,7-二噻吩-2-基-苯并[1,2,5]噻二唑(化合物9a)
将4,7-二溴-2,1,3-苯并噻二唑(化合物8)(2g,6.8mmol)和三丁基(2-噻吩基)锡烷(5.2mL,16.4mmol)放入干式THF(50mL)中,一边搅拌一边向其中添加PdCl2(PPh3)2(97mg,2摩尔%)。将混合物在氮气氛围下回流3小时。在减压下除去溶剂,将残渣在硅胶上进行柱层析(CH2Cl2∶己烷=1∶2,Rf=0.32)来精制后,用乙醇进行重结晶化,得到了红色-橙色针状的目标化合物(收率88%)。
熔点:124-125℃
1H NMR(CDCl3):δ8.10(d,2H,J=2.4Hz),7.84(s,2H),7.45(d,2H,J=4.5Hz),7.21(dd,2H,J=3.9和5.1Hz).
13C NMR(CDCl3):δ153.0,139.8,128.4,127.9,127.2,126.4,126.2.
对C14H8N2S3的理论值:C,55.97;H,2.68,实测值:C,55.78;H,2.71。
(1-2)4-(5-溴噻吩-2-基)-7-(噻吩-2-基)苯并[1,2,5]噻二唑(化合物4a)
将4,7-二-2-噻吩基-2,1,3-苯并噻二唑(化合物9a)(350mg,1.17mmol)加入到乙酸(50mL)与CH2Cl2(50mL)的混合物中,一边在常温下搅拌,一边向其中经30分钟以少量添加NBS(229mg,1.28mmol)。将溶液搅拌整夜后,将混合物倒入水(100mL)中,将分离的有机层用硫酸镁干燥后,蒸发溶剂。将粗产物在硅胶上通过快速柱层析(CH2Cl2∶己烷=1∶4,Rf=0.46)分离,得到了橙色粉末状的目标化合物(收率70%)。
熔点:126℃
1H NMR(CDCl3):δ8.12(d,1H,J=3.3Hz),7.82(m,3H),7.47(d,1H,J=5.1Hz),7.21(dd,1H,J=3.9和4.5Hz),7.15(d,1H,J=3.9Hz).
13C NMR(CDCl3):δ152.6,152.3,140.8,139.3,130.8,128.2,127.8,127.2,127.1,126.4,125.7,125.2,125.0,114.6.
对C14H7BrN2S3的理论值:C,44.33;H,1.86,实测值:C,44.46;H,2.00。
(1-3)双(9,9-二甲基-9H-芴-2-基)-{4-[5-(7-噻吩-2-基苯并[1,2,5]噻二唑-4-基)-噻吩-2-基]-苯基}胺(化合物6a)
将化合物4a(170mg,0.45mmol)、双(9,9-二甲基-9H-芴-2-基)-[4-(4,4,5,5-四甲基-[1,3,2]-二氧杂硼烷-2-基)-苯基]胺(化合物5)(272mg,0.45mmol)、Pd(PPh3)4(56mg)和Na2CO3(50mg)溶于甲苯(20mL)、乙醇(20mL)和水(20mL)的混合物中,将得到的混合物回流12小时。在减压条件下蒸发溶剂后,向其中添加水(50mL)和二氯甲烷(50mL)。分离有机层,用硫酸镁进行干燥。在减压条件下除去溶剂,作为洗脱液使用CH2Cl2,在硅胶上进行柱层析(Rf=0.63),得到了目标化合物(收率68%)。
熔点:137℃
1H NMR(CDCl3):δ8.13(d,2H,J=3.3Hz),7.88(s,2H),7.68-7.13(m,6H),7.46-7.13(m,15H),1.44(s,12H).
13C NMR(CDCl3):δ155.3,153.7,152.8,152.6,147.9,147.1,145.7,139.6,139.1,139.0,137.8,134.6,134.2,128.9,128.2,127.5,127.2,126.9,126.7,126.1,126.0,125.7,125.2,123.8,123.5,123.3,122.7,120.8,119.6,119.0,47.0,29.8.
对C50H37N3S3的理论值:C,77.38;H,4.81,实测值:C,77.98;H,4.84。
(1-4)5-[7-(5-{4-[双(9,9-二甲基-9H-芴-2-基)-氨基]苯基}噻吩-2-基)苯并[1,2,5]噻二唑-4-基]噻吩-2-甲醛(化合物7a)
将化合物6a溶于N,N-二甲基甲酰胺(DMF,5mL)后,在0℃下向其中添加氧氯化磷,在80℃下搅拌24小时。在真空下除去DMF后,将反应混合物用乙酸钠进行中和,用二氯甲烷进行萃取。作为洗脱液使用二氯甲烷,将粗产物用柱层析(Rf=0.34)进行精制,得到了目标化合物(收率65%)。
熔点:145℃
1H NMR(CDCl3):δ9.97(s,1H),8.20(m,2H),8.01(d,1H,J=7.9Hz),7.91(d,1H,J=8.1Hz),7.84(d,1H,J=3.9Hz),7.68-7.59(m,6H),7.42-7.12(m,13H),1.43(s,12H).
13C NMR(CDCl3):δ182.2,155.7,155.1,155.8,147.4,146.9,145.1,143.5,143.1,143.3,142.7,139.8,138.2,134.4,130.2,130.0,129.1,129.0,128.2,127.0,126.7,126.4,125.7,124.8,123.6,123.4,122.4,120.8,119.5,118.3,46.7,29.6.
对C51H37N3OS3的理论值:C,76.18;H,4.64,实测值:C,76.02;H,4.50。
(1-5)3-{5-[7-(5-{4-[双(9,9-二甲基-9H-芴-2-基)-氨基]苯基}噻吩-2-基)苯并[1,2,5]噻二唑-4-基]噻吩-2基}-2-氰基丙烯酸(化合物1a,JK-68)
将化合物7a(48mg,0.06mmol)和氰基乙酸(10mg,0.12mmol)的混合物真空干燥后,向其中添加CHCl3和哌啶,回流15小时。在反应液中添加水(50ml),分离有机层,用硫酸镁进行干燥。接着,在减压下除去溶剂,在硅胶上进行柱层析(CH2Cl2∶甲醇=6∶1,Rf=0.27),得到了目标化合物(收率58%)。
熔点:290℃
1H NMR(DMSO-d6):δ8.49(s,1H),8.24-8.04(m,5H),7.74-7.49(m,9H),7.31(m,6H),7.10(m,4H),1.37(s,12H).
13C NMR(DMSO-d6):δ169.9,163.1,154.9,153.2,151.7,151.5,147.3,146.4,145.7,143.5,140.9,138.4,138.2,136.6,135.6,134.2,129.6,129.4,127.8,127.1,127.0,126.8,126.5,126.0,125.0,124.1,123.7,123.3,123.2,122.7,121.3,119.7,119.1,118.7,46.5,26.7.
对C54H38N4O2S3的理论值:C,74.46;H,4.40,实测值:C,74.11;H,4.30。
实施例2化合物1b(JK-69)的合成
[化合物1b]
(2-1)4,7-双-(3-己基噻吩-2-基)苯并[1,2,5]噻二唑(化合物9b)
将4,7-二溴-2,1,3-苯并噻二唑(化合物8)(673mg,2.3mmol)和2-(3-己基噻吩-2-基)-4,4,5,5-四甲基-[1,3,2]-二氧杂硼烷(1.35g,4.59mmol)、Pd(PPh3)4(266mg,5摩尔%)和Na2CO3(488mg,4.6mmol)溶解于甲苯(30mL)、乙醇(20mL)和水(20mL)的混合物中,将得到的混合物回流20小时。在减压条件下蒸发溶剂后,向其中添加水(50mL)和二氯甲烷(50mL)。分离有机层,用硫酸镁进行干燥。在减压条件下除去溶剂,在硅胶上进行柱层析(CH2Cl2∶己烷=1∶2,Rf=0.41),得到了目标化合物(收率70%)。
熔点:124-125℃
1H NMR(CDCl3):δ7.64(s,2H),7.44(d,2H,J=5.7Hz),7.10(d,2H,J=5.1Hz),2.66(t,4H,J=7.8Hz),1.62(m,2H),1.20(m,12H),0.80(t,6H,J=6.9Hz).
13C NMR(CDCl3):δ154.4,141.8,132.3,130.0,129.4,127.6,126.0,31.7,30.8,29.5,29.2,22.7,14.2.
对C26H32N2S3的理论值:C,66.62;H,6.88,实测值:C,66.76;H,6.43。
(2-2)4-(5-溴-3-己基噻吩-2-基)-7-(3-己基噻吩-2-基)苯并[1,2,5]噻二唑(化合物4b)
代替化合物9a使用化合物9b,按照与上述实施例1的(1-2)相同的方法得到了目标化合物(收率56%)。
熔点:126℃
1H NMR(CDCl3):δ7.63(m,2H),7.44(d,1H,J=5.1Hz),7.11(d,1H,J=4.5Hz),7.07(d,1H,J=1.2Hz),2.65(m,4H),1.61(m,4H),1.21(m,12H),0.81(m,6H).
13C NMR(CDCl3):δ154.2,153.9,142.3,141.8,133.8,132.0,131.9,129.8,129.2,127.9,126.1,126.0,113.0,31.6,31.5,30.7,30.5,29.4,29.1,29.0,22.5,14.1.
对C26H31BrN2S3的理论值:C,57.02;H,5.71,实测值:C,56.90;H,5.53。
(2-3)双(9,9-二甲基-9H-芴-2-基)-(4-{4-己基-5-[7-(3-己基噻吩-2-基)苯并[1,2,5]噻二唑-4-基]-噻吩-2-基}苯基)胺(化合物6b)
代替化合物4a使用化合物4b,按照与上述实施例1的(1-3)相同的方法得到了目标化合物(收率71%)。
熔点:100℃
1H NMR(CDCl3):δ7.74-7.64(m,8H),7.50-7.16(m,15H),2.76(m,4H),1.74(m,4H),1.51(s,12H),1.29(m,12H),0.90(m,6H).
13C NMR(CDCl3):δ155.2,154.4,154.2,153.6,147.6,147.1,144.5,142.9,141.7,139.0,134.4,132.3,131.1,130.0,129.6,129.3,128.5,127.5,127.3,127.1,126.6,126.0,124.7,123.9,123.4,122.6,120.8,119.5,118.8,46.9,31.7,30.8,29.8,29.5,29.2,29.1,27.1,22.7,22.6,14.2,14.1.
对C62H61N3S3的理论值:C,78.85;H,6.51,实测值:C,78.69;H,6.88。
(2-4)5-[7-(5-{4-[双(9,9-二甲基-9H-芴-2-基)-氨基]苯基}-3-己基噻吩-2-基)苯并[1,2,5]噻二唑-4-基]-4-己基噻吩-2-甲醛(化合物7b)
代替化合物6a和过量的氧氯化磷(10当量)使用化合物6b,按照与上述实施例1的(1-4)相同的方法得到了目标化合物(收率60%)。
熔点:93℃
1H NMR(CDCl3):δ9.96(s,1H),7.79-7.13(m,22H),2.70(m,4H),1.66(m,4H),1.44(s,12H),1.25(m,12H),0.87(m,6H).
13C NMR(CDCl3):δ183.1,155.2,154.1,153.8,153.7,147.8,147.1,145.1,143.4,143.2,143.0,142.7,139.0,138.0,134.5,130.6,130.5,129.2,129.1,128.3,127.2,126.7,126.6,125.7,124.9,123.8,123.5,122.6,120.8,119.6,118.9,47.0,31.7,31.6,30.8,30.5,29.9,29.5,29.3,29.1,27.2,22.7,22.6,14.2,14.1.
对C63H61N3OS3的理论值:C,77.82;H,6.32,实测值:C,77.87;H,6.43。
(2-5)3-{5-[7-(5-{4-[双(9,9-二甲基-9H-芴-2-基)-氨基]苯基}-(3-己基噻吩-2-基)苯并[1,2,5]噻二唑-4-基]-4-己基噻吩-2基}-2-氰基丙烯酸(化合物1b,JK-69)
代替化合物7a使用化合物7b,按照与上述实施例1的(1-5)相同的方法得到目标化合物(收率64%)。
熔点:224℃
1H NMR(DMSO-d6):δ8.32(s,1H),7.75-7.11(m,22H),3.42(m,4H),2.45(m,4H),1.36(s,12H),1.10(m,12H),0.71(m,6H).
13C NMR(DMSO-d6):δ168.5,162.7,155.1,153.5,151.6,151.3,147.7,146.4,145.5,143.3,140.6,138.0,137.7,136.5,135.8,134.1,129.6,129.3,127.3,127.1,126.9,126.8,126.3,126.0,124.9,124.0,123.6,123.1,123.0,122.7,121.8,120.0,118.9,117.7,47.5,33.7,32.6,30.7,30.5,30.0,29.6,29.2,29.1,27.0,22.0,21.6,13.9,13.8.
对C66H62N4O2S3的理论值:C,76.26;H,6.01,实测值:C,76.61;H,6.31。
实施例3染料敏化太阳能电池的制造
为了评价根据本发明的染料化合物的电流-电压特性,利用10+4μm TiO2双层制造太阳能电池。将TiO2糊剂(Solaronix,Ti-Nanoxide T/SP)在掺氟二氧化锡(FTO)玻璃基板上进行丝网印刷,制造10μm厚度的第一TiO2透明层,为了光散射,另外用糊剂(CCIC,PST-400C)制造4μm厚度的第二TiO2散射层。将该TiO2电极在70℃下用40mM TiCl4溶液处理30分钟,在500℃下烧结30分钟。接着,将该TiO2电极分别浸渍到上述实施例1和2中制造的本发明的染料化合物JK-68溶液(含有10mM的鹅脱氧胆酸的四氢呋喃中含有0.3mM染料)和JK-69溶液(四氢呋喃中含有0.3mM染料)中后,在常温下放置24小时。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),以80℃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3-甲氧基丙腈(MPN)中溶解有1,2-二甲基-正丙基碘化咪唑(DMPImI)(0.6M)、I2(0.1M)、NMBI(0.5M)和聚偏氟乙烯-六氟丙烯共聚物(PVDF-HFP)(5重量%)的溶液。
试验例 实施例中制造的染料以及包含该染料的染料敏化太阳能电池的物性测定
测定上述实施例1和2中制造的有机染料的物性并表示在图1-3中,测定包括上述有机染料的染料敏化太阳能电池的物性并表示在图4-7中,并将其结果整理在下表1来表示。
表1
将实施例1和2中制造的染料JK-68和JK-69各自的在四氢呋喃(THF)中测定的吸光和发光光谱表示在图1中。JK-68的吸光光谱因共轭系统的π-π转移而在534nm和374nm中显示2个最大吸光峰,在噻吩上具有己基的JK-69的情况下,在468nm和370nm显示最大吸光峰。像这样,与JK-69相比,JK-68显示相当的红移,将染料JK-68和JK-69各自吸附于TiO2电极的情况下,也显示与上述类似的红移。
将对实施例1和2中制造的染料JK-68和JK-69各自以对于B3LYP/3-21G的TD-DFT计算的最佳结构表示在图2中(a)JK-68和b)JK-69)。JK-68的基态结构在N,N-双(9,9-二甲基芴-2-基)苯胺和噻吩基单元之间具有20.6度扭转(twist),噻吩基和苯并噻二唑单元之间具有5.8度的二面角。JK-69的情况下,分别具有21.2度和44.4度的扭转角。
因此,判断为与JK-69相比时,JK-68的相当的红移的原因在于经全部共轭系统的位移。
将对实施例1和2中制造的染料JK-68和JK-69各自利用B3LYP/3-21G而计算的几何形态以HOMO和LUMO的等密度(isodensity)表面图表示在图3中(a)JK-68和b)JK69)。
另外,将实施例3中制造的DSSC(使用了含有溶解在3-甲氧基丙腈(MPN)中的1,2-二甲基-正丙基碘化咪唑(DMPImI)(0.6M)、I2(0.1M)、NMBI(0.5M)和聚偏氟乙烯-六氟丙烯共聚物(PVDF-HFP)(5重量%)的聚合物凝胶电解质)的光电池性能(单色入射光子-对-电流转换效率(IPCEs)的谱图)及光电流密度-电压(J-V)曲线表示在图4中。分别含有染料JK-68和JK-69的太阳能电池显示了9.58和12.03mA cm-2的短路光电流密度(JSC)、0.643和0.720V的开路电压(VOC)、0.75和0.76的填充粒子(fill factor)以及4.66和6.61%的光电转换效率。JK-69的光电转换效率6.61%显著高于目前报告的6.1%,这样的JK-69的高光电转换效率和高开路电压等是噻吩单元上取代的己基的导入所致。
将实施例3中制造的DSSC(使用了含有溶解在MPN中的DMPIml(0.6M)、I2(0.1M)、NMBI(0.5M)和PVDF-HFP(5重量%)的聚合物凝胶电解质)在加速化的老化条件(60℃,过多的可见光照射-AM 1.5G,100mWcm-2)下维持1000小时,并测定随着时间的短路光电流密度(JSC)、开路电压(VOC)、填充粒子(fill factor)和光电转换效率各自的变化,表示在图5中(▲:JK-68,■:JK-69)。此时,在进行照明的期间,使420nm截止(cut-off)滤光片位于电池表面上。由图5可知,含有JK-69的电池的情况下显示出了特别优异的长期稳定性。
测定实施例3中制造的DSSC(为了进行比较,制造含有以往的染料JK-2的染料敏化太阳能电池来进行比较)的电子放出系数(a)和寿命(b),表示在图6中。
另外,将实施例3中制造的DSSC(为了进行比较,制造含有以往的染料JK-2的染料敏化太阳能电池来进行比较)的电化学阻抗(impedance)谱在明条件(照明100mWcm-2)(a)和暗条件(b)下进行测定,表示在图7中。
由上述多种结果可知,含有低带隙发色团的本发明的新型染料显示出了优异的摩尔吸光系数、Jsc(短路光电流密度)、光电转换效率和稳定性,从而可以大幅度提高太阳能电池的效率。特别是利用了JK-69的太阳能电池显示明显优异的光电转换效率和稳定性。
产业上的利用可能性
本发明的新型噻吩系染料显示了比以往的金属配位化合物染料和有机染料更高的光电池性能、即更高的摩尔吸光系数、Jsc(短路光电流密度)和光电转换效率,并具有优异的稳定性,能够大幅度提高太阳能电池的效率。
Claims (11)
4.一种由化学式1a或1b表示的染料的制造方法,其特征在于,包括:
(1)使下述化学式8的化合物与锡烷基噻吩或2-(3-己基噻吩-2-基)-4,4,5,5-四甲基[1,3,2]二氧杂硼烷进行斯泰尔或铃木偶联反应,制造下述化学式9a或9b的化合物,
(2)在有机溶剂中,使化学式9a或9b的化合物与N-溴代琥珀酰亚胺反应而进行溴化,制造下述化学式4a或4b的化合物,
(3)使化学式4a或4b的化合物与下述化学式5的化合物进行铃木偶联反应,制造下述化学式6a或6b的化合物,
(4)通过维尔斯迈尔-哈克反应使化学式6a或6b的化合物进行醛化,制造下述化学式7a或7b的化合物,
(5)在氯仿中,在哌啶存在下,使化学式7a或7b的化合物与氰基乙酸反应,
化学式8
化学式9a
R=H
化学式9b
R=己基
化学式4a
R=H
化学式4b
R=己基
化学式5
化学式6a
R=H
化学式6b
R=己基
化学式7a
R=H
化学式7b
R=己基
化学式1a
R=H
化学式1b
R=己基。
5.根据权利要求4所述的染料的制造方法,其中,所述步骤(2)中使用的有机溶剂是乙酸和二氯甲烷的混合物。
6.一种染料增感光电转换元件,其特征在于,含有担载有权利要求1所述的噻吩系染料的氧化物半导体微粒。
7.根据权利要求6所述的染料增感光电转换元件,其中,在包合物存在下,在所述氧化物半导体微粒上担载噻吩系染料。
8.根据权利要求7所述的染料增感光电转换元件,其中,所述氧化物半导体微粒含有二氧化钛作为必要成分。
9.根据权利要求7所述的染料增感光电转换元件,其中,所述氧化物半导体微粒的平均粒径为1-500nm。
10.一种染料敏化太阳能电池,其特征在于,含有权利要求6所述的染料增感光电转换元件作为电极。
11.根据权利要求10所述的染料敏化太阳能电池,其中,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;将涂布有糊剂的基板进行烧成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、化学式2或化学式3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2玻璃基板的步骤;形成贯通第2玻璃基板和对电极的孔的步骤;在所述对电极和所述吸附有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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