CN102277007B - 无硫氰酸根配基的光敏剂及敏化染料太阳能电池 - Google Patents
无硫氰酸根配基的光敏剂及敏化染料太阳能电池 Download PDFInfo
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- 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
- Y02E10/549—Organic PV cells
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Abstract
本发明是一种无硫氰酸根配基的光敏剂及敏化染料太阳能电池,该光敏剂包含以式(a)表示的化学式:RuL1L2L3 式(a)其中,Ru为钌,L1、L2及L3为二齿杂环配位基,L1具有以式(b)表示的结构,L2具有以式(b)、式(c)、式(d)或式(e)表示的结构,以及L3具有以式(c)、式(d)或式(e)表示的结构;式(b) 式(c)式(d) 式(e)其中,R1至R18选自氢原子、卤素、芳基、烯基、具有C1-C20的烷基、环烷基、炔基、氰基、氟甲烷基、烷氨基、胺基、烷氧基、杂芳基、具有卤素取代基的芳基、具有卤素取代基的芳烷基、具有卤代烷基取代基的芳基、具有卤代烷基取代基的芳烷基及具有芳基的C1-C20烷基及以上的组合所组成的群组的其中之一。上述的光敏剂可作为制备敏化染料太阳能电池用的染料敏化剂。
Description
技术领域
本发明是关于一种光敏剂及其敏化染料太阳能电池,特别是一种具备较佳光电转换效率的光敏剂及其敏化染料太阳能电池。
背景技术
由于石化燃料为一次性能源,其不仅有耗竭的可能,且使用石化燃料所排放的废气亦造成空气污染,甚至是造成地球暖化的元凶之一。因此,寻求替代能源以降低对石化燃料的依赖是目前刻不容缓的课题。在绿色能源的发展上,太阳能的来源最为干净、丰沛,且无需挖采、精制,因此太阳能成为新能源开发利用中最活跃的领域。
敏化染料太阳能电池(dye-sensitized solar cell,DSSC)的工艺简单,且制造成本较现有的硅基材料太阳能电池低廉,因此,敏化染料太阳能电池被视为继硅基材料太阳能电池之后最具潜力的太阳能电池之一。由于光敏染料性质的优劣直接影响敏化染料太阳能电池的光电转换效率,因此光敏染料即成为敏化染料太阳能电池的研究重点之一。
目前使用较为广泛的光敏染料为N719染料,其具备式(I)所示的结构。然而,N719染料的吸收光谱范围与太阳光谱的匹配度不佳,其对于波长600nm以后的光谱响应较差,因此无法有效利用此波段的太阳光能。此外,在现有的N719染料,由于硫氰酸根阴离子(NCS-,thiocyanate)配位基的配位键强度较弱。因此,若能用其它更有效且稳定的螯合配基或发色团以取代硫氰酸根配位基(NCS-),应可以增加敏化染料太阳电池的效率及寿命。
综上所述,由于光敏染料性质的优劣直接影响敏化染料太阳能电池的光电转换效率,因此研发具备较佳光电转换效率的光敏染料仍是目前极需努力的目标。
发明内容
本发明的目的为提供一种光敏剂,其具有二齿杂环螯合配位基以取代传统的硫氰酸根配位基,以达到更佳的光电转换效率。
依据本发明一方面提供一种光敏剂,该光敏剂包含以式(a)表示的化学式:
RuL1L2L3 式(a)
其中,Ru为钌,L1、L2及L3为二齿杂环配位基,L1具有以式(b)表示的结构,L2具有以式(b)、式(c)、式(d)或式(e)表示的结构,以及L3具有以式(c)、式(d)或式(e)表示的结构;
式(c)
式(d) 式(e)
其中,R1至R18各自独立地选自氢原子(H)、卤素(halogen)、芳基(aryl group)、烯基(alkenyl)、具有C1-C20的烷基(C1-C20alkyl group)、环烷基(cycloalkylgroup)、炔基(alkynyl)、氰基(cyano,CN)、氟甲烷基(trifluoromethyl,CF3)、烷氨基(alkylamino)、胺基(amino)、烷氧基(alkoxy)、杂芳基(heteroaryl)、具有卤素取代基的芳基(halogen substituted aryl group)、具有卤素取代基的芳烷基(halogen substitutedaromatic group)、具有卤代烷基取代基的芳基(haloalkyl substituted aryl group)、具有卤代烷基取代基的芳烷基(haloalkyl substituted aromatic group)及具有芳基的C1-C20烷基(aryl substituted C1-C20 alkyl group)及以上的组合所组成的群组的其中之一。
本发明的另一目的为提供一种敏化染料太阳能电池,其具有更佳的光电转换效率,并增加太阳能电池的效率及寿命。
依据本发明另一方面提供一种敏化染料太阳能电池,该敏化染料太阳能电池包含一第一电极、一第二电极以及一电解质。第一电极包含一透明导电基板以及一多孔性薄膜,其中多孔性薄膜为一半导体材料设置于透明导电基板的一表面,且载有前述的光敏剂。电解质则设置于多孔性薄膜以及第二电极之间。
本发明的有益技术效果是:本发明的光敏剂具有二齿杂环配位基,其不具硫氰酸根配位基,因此相较于N719具有具有较高的光电转换效率η与元件寿命,因此利用本发明的光敏剂所制备的敏化染料太阳能电池具备较佳的整体电池元件效能表现。
附图说明
本发明上述及其它态样、特性及优势可由以下结合附图对本发明的较佳实施例的详细说明而可获得更加清楚的了解,其中:
图1为显示本发明一较佳实施例的光敏剂以及现有的N719染料的吸收光谱的曲线图。
图2为显示本发明一较佳实施例的敏化染料太阳能电池的结构的示意图。
具体实施方式
本发明的一较佳实施例的光敏剂具有以式(a)表示的化学式:
RuL1L2L3 式(a)
其中,Ru为钌,L1、L2及L3为二齿杂环配位基,L1具有以式(b)表示的结构,L2具有以式(b)、式(c)、式(d)或式(e)表示的结构,以及L3具有以式(c)、式(d)或式(e)表示的结构:
式(b) 式(c)
其中,R1至R18各自独立地可独立地选自由氢(H)、卤素(halogen)、芳基(arylgroup)、烯基(alkenyl)、具有C1-C20的烷基(C1-C20alkyl group)、环烷基(cycloalkyl group)、炔基(alkynyl)、氰基(cyano,CN)、氟甲烷基(trifluoromethyl,CF3)、烷氨基(alkylamino)、胺基(amino)、烷氧基(alkoxy)、杂芳基(heteroaryl)、具有卤素取代基的芳基(halogen substituted aryl group)、具有卤素取代基的芳烷基(halogensubstituted aromatic group)、具有卤代烷基取代基的芳基(haloalkyl substituted arylgroup)、具有卤代烷基取代基的芳烷基(haloalkyl substituted aromatic group)及具有芳基的C1-C20烷基(aryl substituted C1-C20alkyl group)及以上的组合所组成的群组的其中之一。
举例而言,本发明的光敏剂包含、但不限于下列式(f)至式(1)化合物的核心配位结构:
式(f) 式(g)
式(h) 式(i)
式(j) 式(k)
式(1)
于一实施例中,式(b)的R3及R6各自独立为羧基;式(c)的R14,式(d)的R15、R17及式(e)的R18为CF3。因此本发明的较佳化合物包含下列式(m)至式(s)结构。
式(m)
式(n)
式(o) 式(p)
式(q) 式(r)
式(s)
于一实施例中,式(c)中的R11、R13及式(d)中的R11、R16各自独立地选自芳基、杂芳基、具有卤素取代基的芳基、具有卤素取代基的芳烷基、具有卤代烷基取代基的芳基、具有卤代烷基取代基的芳烷基及具有芳基的C1-C20烷基。较佳者,(c)中的R11、R13及式(d)中的R11、R16各自独立地选自噻吩(thiophene)、5-(噻吩-2-基)噻吩(5-(thiophen-2-yl)thiophene)、具噻吩取代基的C1-C20的烷基、具5-(噻吩-2-基)噻吩取代基的C1-C20的烷基、1-叔丁基-4-[(1E)-3-异丙烯基-二甲基]苯(1-tert-butyl-4-[(1E)-prop-l-en-1-yl]benzene)及N,N-二苯苯胺(N,N-diphenylaniline)所组成的群组的其中之一。举例而言,(c)中的R11、R13及式(d)中的R11、R16包含下列化学式,其中R’为C1-C20烷基或C1-C20环烷基(cycloalkyl group):
化合物实施例1
在一较佳实施例中,本发明的光敏剂具有化学式(t),其中,光敏剂TFRS-1中的R为氢原子;光敏剂TFRS-2中的R为5-己基噻吩(5-hexylthiophene);光敏剂TFRS-3中的R为5-己基[2,2′]双噻吩(5-hexyl[2,2’]bithiophene)。
式(t)
光敏剂TFRS-1、TFRS-2及TFRS-3可由下列方程式制备:
具体说,在TFRS-1的合成方面,将2-(3-(trifluoromethyl)-1H-pyrazol-5-yl)pyridine(45mg,0.21mmol)与Ru(diethyl2,2′-bipyridine-4,4′-dicarboxylate)(p-cymene)Cl(60mg,0.10mmol)溶于2-methoxyethanol(20mL)溶剂中,在130℃回流12小时。随后用真空系统将溶剂抽干,将固体以二氯甲烷溶解,用去离子水清洗三次,取有机层,经干燥再用旋转浓缩机将有机溶剂抽干,以CH2Cl2∶EA=1∶2进行管柱分离得到产物。最后,将固体溶于丙酮中,加入1M NaOH溶液(5mL)。再在氮气下,于100℃下加热24小时,以进行水解。反应结束后,移除有机溶剂,加入10mL的去离水,使用2NHCl溶液调整pH值至3,此时可得到咖啡色固体沉淀。用少许甲醇溶解后,以Sephadex LH-20管柱做为载体,进行纯化。
在TFRS-2及TFRS-3的合成方面,TFRS-2的pyridyl pyrazole起始物为5-hexylthiophene pyridyl pyrazole(0.20mmol),TFRS-3的pyridyl pyrazole起始物为5-hexylthiophene pyridyl pyrazole,其余步骤则为相同,在此不再赘述。其中TFRS-1的产率为32.4%,TFRS-2的产率为27%,TFRS-3的产率为35%。
化合物TFRS-1的光谱资料:MS(FAB,102Ru):m/z 771(M+1)+.1H NMR(400MHz,d-DMSO,298K):δ8.95(s,1H),8.14(d,J=6.0Hz,1H),7.99(d,J=8.0Hz,1H),7.83(t,J=8.0Hz,1H),7.78(d,J=5.2Hz,1H),7.28(s,1H),7.21(t,J=6.0Hz,1H),7.64(d,J=5.2Hz,1H).Anal.Calcd for C30H18F6N8O4Ru·4H2O:C,42.81;N,13.31;H,3.11.Found:C,43.08;N,12.96;H,3.18.
化合物TFRS-2的光谱数据:MS(FAB,102Ru):m/z 1103(M+1)+.1H NMR(d6-DMSO,400MHz)δ:8.96(s,2H),8.27(d,J=6.4Hz,2H),8.22(s,2H),7.79(d,J=6Hz,2H),7.74(d,J=3.2Hz,2H),7.45(s,2H),7.42(d,J=6Hz,2H),7.05(d,J=6Hz,2H),6.96(d,J=3.2Hz,2H),2.82(t,J=7.2Hz,4H),1.61~0.83(m,22H).Anal.Calcd for C50H46F6N8O4RuS2·H2O:C,53.61;N,10.00;H,4.32.Found:C,53.93;N,9.79;H,4.36.
化合物TFRS-3的光谱数据:MS(FAB,102Ru):m/z 1267(M+1)+.1H NMR(d6-DMSO,400MHz)δ:8.94(s,2H),8.28~8.26(m,4H),7.86(d,J=3.6Hz,2H),7.79(d,J=6Hz,2H),7.48~7.52(m,4H),7.34(d,J=3.6Hz,2H),7.20(d,J=3.6Hz,2H),7.07(d,J=6.4Hz,2H),6.83(d,J=3.6Hz,2H),2.76(t,J=7.6Hz,4H),1.61~1.24(m,16H),0.83(t,J=7.2Hz,6H).Anal.Calcd for C58H50F6N8O4RuS4·4H2OC,52.05;N,8.37;H,4.37.Found:C,52.28;N,8.28;H,4.28.
请参照图1,其为具有式(t)结构的本发明的光敏剂以及N719染料的吸收光谱。图1所示的吸收光谱可知,相较于N719染料,本发明的光敏剂TFRS-2及TFRS-3在大部分的波长区段中具有较佳的吸光系数。
化合物实施例2
式(m)
具体说,在化合物(m)的合成方面,将Dichloro(p-cymene)ruthenium(II)(75mg,0.117mmol)与4,4’-bis(ethoxycarbonyl)-2,2’-bipyridine(146mg,0.487mmol)于溶于DMF中加热140℃反应3小时,随后加入2-(3-(trifluoromethyl)-lH-pyrazol-5-yl)pyridine(49mg,0.230mmol)继续反应,在140℃加热12小时。反应结束后用真空系统将溶剂抽干,将固体以二氯甲烷溶解,用去离子水清洗三次,取有机层,经干燥再用旋转浓缩机将有机溶剂抽干,以CH2Cl2∶ACN=4∶1进行管柱分离得到产物。最后,将固体溶于丙酮中,加入1MNaOH溶液(1mL)。在氮气下,于100℃下加热3小时,以进行水解。反应结束后,移除有机溶剂,加入10mL的去离水,使用0.1M HNO3溶液调整pH值至3,此时可得到咖啡色固体沉淀。用少许甲醇溶解后,加入0.1M tetrabutylammoniumhydroxide(0.33mmol),最后以Sephadex LH-20管柱做为载体,进行纯化,产率为46%。
化合物(m)的光谱资料:MS(FAB,102Ru):m/z 801(M+1)+.1H NMR(400MHz,d-MeOD,298K):δ9.02(s,1H),9.00(s,2H),8.99(s,H),8.00(d,J=4.0Hz,1H),7.94(d,J=4.0Hz,1H),7.87(d,J=4.0Hz,2H),7.82(m,J=4.0Hz,4H),7.745(d,J=4.0Hz,1H),7.695(d,J=4.0Hz,1H),7.465(d,J=4.0Hz,1H),7.10(t,J=8.0Hz,1H).,3.22(q,J=8.0Hz,16H),1.64(m,16H),1.39(m,16H),0.99(t,J=6.0Hz,24H).
化合物实施例3
式(n)-1
具体说,在化合物(n)-1的合成方面,将Dichloro-4,4‘-bis(ethoxycarbonyl)-2,2’-bipyridine-ruthenium(II)化合物(100mg,0.129mmol)与3,5-bis(trifluoromethl)-2-(2’-pyridyl)pyrrol(42mg,0.150mmol)溶于Ethanol(20mL)溶剂中,在100℃回流14小时。反应结束后过滤掉固体,随后用真空系统将溶剂抽干,将固体以二氯甲烷溶解,用去离子水清洗三次,取有机层,经干燥再用旋转浓缩机将有机溶剂抽干,以CH2Cl2∶MeOH=9∶1进行管柱分离得到产物。最后,将固体溶于丙酮中,加入1M NaOH溶液(1mL)。在氮气下,于100℃下加热3小时,以进行水解。反应结束后,移除有机溶剂,加入10mL的去离水,使用0.1M HNO3溶液调整pH值至3,此时可得到咖啡色固体沉淀。用少许甲醇溶解后,以Sephadex LH-20管柱做为载体,进行纯化,产率为54%。
的化合物(n)-1的光谱资料:1H NMR(400MHz,d-DMSO,298K):δ9.139(s,2H),9.069(s,1H),9.018(s,1H),7.962(s,broad,3H),7.865(s,broad,1H),7.805(s,broad,2H),7.677(s,broad,1H),7.567(s,broad,3H),7.321(s,broad,1H),7.08(s,broad,1H),6.879(s,1H).
化合物(n)-2合成方法
具体说,在化合物(n)-2的合成方面,将Dichloro-4,4‘-bis(ethoxycarbonyl)-2,2’-bipyridine-ruthenium(II)complex(100mg,0.129mmol)与3,5-dimethyl-2-(2’-pyridyl)pyrrol(22mg,0.129mmol)溶于Ethanol(20mL)溶剂中,在100℃回流12小时。反应结束后过滤掉固体,随后用真空系统将溶剂抽干,将固体以乙酸乙酯溶解,用去离子水清洗三次,取有机层,经干燥再用旋转浓缩机将有机溶剂抽干,以CH2Cl2∶MeOH=9∶1进行管柱分离得到产物。最后,将固体溶于乙腈中,加入0.1M tetrabutylammoniumhydroxide溶液(1mL)。在氮气下,室温下搅拌2小时,以进行水解。反应结束后,移除有机溶剂,加入10mL的去离水,使用0.1M HNO3溶液调整pH值至3,此时可得到咖啡色固体沉淀。用少许甲醇溶解后,以Sephadex LH-20管柱做为载体,进行纯化。
化合物(n)-2的光谱资料:1H NMR(400MHz,d-DMSO,298K):δ8.988(s,1H),8.949(s,2H),8.939(s,1H),8.074(d,J=5.6Hz,1H),
7.800(m,broad,5H),7.649(dd,J=4.4Hz,1.2Hz,2H),7.477(m,broad,2H),7.567(d,J=5.6Hz,1H),7.321(s,broad,1H),
6.506(td,户4Hz,2Hz,1H),2.027(s,3H),1.268(s,3H)
敏化染料太阳能电池效能请参照图2,本发明的一较佳实施例的敏化染料太阳能电池包含一第一电极11、一第二电极12以及一电解质13。第一电极11包含一透明导电基板111以及一多孔性薄膜112。多孔性薄膜112设置于透明导电基板111的一表面,且载有一光敏剂113。多孔性薄膜112为一半导体材料,例如TiO2。于一实施例中,透明导电基板111可为一FTO玻璃(F dopes SnO2 glass)。电解质13则设置于多孔性薄膜112以及第二电极12之间。光敏剂113的结构如前所述,在此不再赘述。
利用前述的光敏剂TFRS-1~TFRS-3制备本发明的敏化染料太阳能电池,其特性如表一所示,其中第一电极11包含光敏剂TFRS-1~TFRS-3、TiO2多孔性薄膜以及FTO玻璃;第二电极为Pt电极,例如:镀有Pt金属或其它任何导电材料,例如:碳黑或石墨,的一般透光材料;电解质则是由以下成分所组成的混合物:0.6M butylmethylimidazolium iodide(BMII),0.03M I2,0.10M guanidiniumthiocycanate,以及0.50M tert-butylpyridine溶于acetonitrile及valeronitrile的混合溶液之中(容积比例85∶15)。
表一
依据表一的结果,本发明的敏化染料太阳能电池具备较佳的光电转换效率η。例如,包含本发明光敏剂TFRS-1~TFRS-3的敏化染料太阳能电池,其光电转换效率η分别为9.18%、9.54%及8.94%;而在相同条件下,N719的光电转换效率η仅约8.56%。
此外,相较于N719,TFRS-1~TFRS-3具有较高效率,例如较高的开路电压、较高的短路电流及较低的填充因子。换言之,本发明的敏化染料太阳能电池能够以较薄的多孔性薄膜制作第一电极,如此可避免电极工艺中的缺陷增加元件开路电压,同时减少光敏剂的使用量以降低工艺成本。
综合上述,本发明的光敏剂具有二齿杂环配位基,其不具硫氰酸根配位基,因此相较于N719具有具有较高的光电转换效率η与元件寿命,因此利用本发明的光敏剂所制备的敏化染料太阳能电池具备较佳的整体电池元件效能表现。
以上所述的实施例仅是为说明本发明的技术思想及特点,其目的在使熟悉此项技术的人士能够了解本发明的内容并据以实施,当不能以其限定本发明的专利范围,即凡是根据本发明所揭示的精神所作的均等变化或修饰,仍应涵盖在本发明的专利范围内。
Claims (10)
1.一种光敏剂,其特征在于包含以式(a)表示的化学式:
RuL1L2L3 式(a)
其中,Ru为钌,L1、L2及L3为二齿杂环配位基,L1具有以式(b)表示的结构,L2具有以式(b)、式(c)、式(d)或式(e)表示的结构,以及L3具有以式(c)、式(d)或式(e)表示的结构;
式(b) 式(c)
式(d) 式(e)
其中,R3及R6各自独立为羧基,R1、R2、R4、R5、R7至R18各自独立地选自氢原子、卤素、芳基、烯基、具有C1-C20的烷基、环烷基、炔基、氰基、氟甲烷基、烷氨基、胺基、烷氧基、杂芳基、具有卤素取代基的芳基、具有卤素取代基的芳烷基、具有卤代烷基取代基的芳基、具有卤代烷基取代基的芳烷基及具有芳基的C1-C20烷基及以上的组合所组成的群组的其中之一。
2.根据权利要求1所述的光敏剂,其特征在于,R14、R15、R17及R18各自独立为CF3。
3.根据权利要求1所述的光敏剂,其特征在于,R11、R13及R16各自独立地选自由芳基、杂芳基、具有卤素取代基的芳基、具有卤素取代基的芳烷基、具有卤代烷基取代基的芳基、具有卤代烷基取代基的芳烷基及具有芳基的C1-C20烷基所组成的群组的其中之一。
5.一种敏化染料太阳能电池,其特征在于,包含:
一第一电极,其包含:
一透明导电基板;以及
一多孔性薄膜,其为一半导体材料,设置于该透明导电基板的一表面,该多孔性薄膜载有一光敏剂;
一第二电极;以及
一电解质,其设置于该多孔性薄膜以及该第二电极之间;
其中,该光敏剂包含以式(a)表示的化学式:
RuL1L2L3 式(a)
其中,Ru为钌,L1、L2及L3为二齿杂环配位基,L1具有以式(b)表示的结构,L2具有以式(b)、式(c)、式(d)或式(e)表示的结构,以及L3具有以式(c)、式(d)或式(e)表示的结构;
式(b) 式(c)
式(d) 式(e)
其中,R3及R6各自独立为羧基,R1、R2、R4、R5、R7至R18各自独立地可独立地选自氢原子、卤素、芳基、烯基、具有C1-C20的烷基、环烷基、炔基、氰基、氟甲烷基、烷氨基、胺基、烷氧基、杂芳基、具有卤素取代基的芳基、具有卤素取代基的芳烷基、具有卤代烷基取代基的芳基、具有卤代烷基取代基的芳烷基、具有芳基的C1-C20烷基及以上的组合所组成的群组的其中之一。
6.根据权利要求5所述的敏化染料太阳能电池,其特征在于,R14、R15、R17及R18各自独立为CF3。
7.根据权利要求5所述的敏化染料太阳能电池,其特征在于,R11、R13及R16各自独立地选自由芳基、杂芳基、具有卤素取代基的芳基、具有卤素取代基的芳烷基、具有卤代烷基取代基的芳基、具有卤代烷基取代基的芳烷基及具有芳基的C1-C20烷基所组成的群组的其中之一。
9.根据权利要求5所述的敏化染料太阳能电池,其特征在于,该半导体材料包含TiO2。
10.根据权利要求5所述的敏化染料太阳能电池,其特征在于,该透明导电基板包含FTO玻璃。
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JP2002173673A (ja) * | 2000-12-05 | 2002-06-21 | Keio Gijuku | 発光材料及び有機el素子 |
WO2009131183A1 (ja) * | 2008-04-24 | 2009-10-29 | シャープ株式会社 | ピリジン系金属錯体、それを用いた光電極およびそれを備えた色素増感太陽電池 |
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Patent Citations (3)
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Non-Patent Citations (5)
Title |
---|
IrIII and RuII Complexes Containing Triazole-Pyridine Ligands: Luminescence Enhancement upon Substitution with β-Cyclodextrin;Marco Felici 等;《Chemistry a european journal》;20091023;第15卷(第60期);13124-13134 * |
Marco Felici 等.IrIII and RuII Complexes Containing Triazole-Pyridine Ligands: Luminescence Enhancement upon Substitution with β-Cyclodextrin.《Chemistry a european journal》.2009,第15卷(第60期), |
俞马宏 等.配体结构对钌(II) 联吡啶配合物的电子结构的影响.《无机化学学报》.1998,第14卷(第3期), |
吕银祥 编.《现代信息材料导论》.《现代信息材料导论》.华东理工大学出版社,2008,(第1版), * |
配体结构对钌(II) 联吡啶配合物的电子结构的影响;俞马宏 等;《无机化学学报》;19980930;第14卷(第3期);276-280 * |
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