CN110218296A - 一种咔唑类聚合物空穴传输材料的结构、合成及其应用 - Google Patents
一种咔唑类聚合物空穴传输材料的结构、合成及其应用 Download PDFInfo
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- CN110218296A CN110218296A CN201910488944.0A CN201910488944A CN110218296A CN 110218296 A CN110218296 A CN 110218296A CN 201910488944 A CN201910488944 A CN 201910488944A CN 110218296 A CN110218296 A CN 110218296A
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Classifications
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
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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
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G2261/10—Definition of the polymer structure
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- C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
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- C08G2261/143—Side-chains containing nitrogen
- C08G2261/1434—Side-chains containing nitrogen containing triarylamine moieties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- C08G2261/41—Organometallic coupling reactions
- C08G2261/411—Suzuki reactions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/51—Charge transport
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Abstract
本发明涉及钙钛矿太阳能电池领域,具体提供了一系列聚咔唑类空穴传输材料的的结构、合成及其应用,所述材料具有分子结构简单,且制备方法具有操作简单、原料价廉易得等特点。由所述的聚合物空穴传输材料空穴迁移率高、成膜性好、具有与钙钛矿材料匹配的能级等优势。所述咔唑类聚合物可作为无掺杂的空穴传输材料应用于钙钛矿太阳能电池器件,可实现18.6%的器件效率,器件具有较好的环境稳定性。
Description
技术领域
本发明属于太阳能电池新材料领域,更具体地,涉及一类钙钛矿太阳能电池聚合物空穴传输层材料设计合成及其应用。
背景技术
清洁能源的开发是未来人类社会低碳经济与可持续发展的基础,而发展低成本、高性能的光电转换技术是实现这一目标的关键之一。在太阳电池的家族中,硅基太阳电池因其转换率高和技术成熟占据了目前太阳电池主要市场份额,但硅太阳电池存在着原材料价格昂贵、生产成本高等缺点。金属卤化物钙钛矿(图1)兼具有机和无机材料在光电性质、溶程加工、低温处理等方面的优势,在光伏领域展现出巨大的应用潜力。2013年,《科学》杂志将钙钛矿太阳电池评选为年度十大科技突破之一。经过短短几年的发展,钙钛矿太阳电池的器件效率已突破24.2%[National Renewable Energy Laboratory(NREL)efficiencychart,http://www.nrel.gov/ncpv/],已经接近薄膜硅电池,但其制造成本较低,成为一种有望进一步降低光伏发电价格的新型光伏体系。在高效的反式p-i-n型钙钛矿太阳能电池(PSCs)中,空穴传输材料(HTMs)作为钙钛矿晶体和电极之间重要的界面层,得到了广泛地研究。HTMs在促进空穴的提取、传输以及抑制钙钛矿和HTM界面处载流子的复合等方面起着非常重要的作用,可以有效地提高器件的性能。目前应用于p-i-n钙钛矿太阳能电池性能最好的聚合物空穴传输材料是PTAA(Science,2018,360,1442.),然而其合成步骤复杂,其价格非常昂贵材料成本高,限制了其未来在钙钛矿电池商业化中的发展。因此,近年来合成工艺简单,原材料价格较低、非掺杂的空穴传输材料,由于其更具商业前景而成为该领域研究的热点。
近来,咔唑类衍生物被作为高效、低成本的HTMs应用于PSCs。本发明将通过将咔唑在不同的活性位点聚合(如2,7位或3,6位),设计合成了一系列聚咔唑类空穴传输材料,可作为非掺杂HTMs应用于反式钙钛矿太阳能电池中。
发明内容
针对以上技术问题,本申请发明人通过将咔唑将咔唑在不同的活性位点聚合(如2,7位或3,6位),设计合成了一系列聚咔唑类空穴传输材料。材料合成成本低廉、成膜性好、空穴迁移率高,可作为无掺杂的空穴传输材料应用于的钙钛矿太阳能电池器件,得到较高的器件效率。
本发明所要解决的技术问题是提供一系列不同连接位点的咔唑类聚合物的结构、合成及其应用。其制备工艺简单、成本低廉,具有优良空穴传输性能。
本发明的系列聚咔唑类空穴传输材料,其特征在于,化学结构式如下:
本发明中所述的系列聚咔唑类空穴传输材料的制备方法,其特征在于,包括如下所述的步骤:
(1)单体合成
化合物1和2的合成:将3,6-二溴咔唑或2,7-二溴咔唑,1-氟-4-碘苯和碳酸铯加入N,N’-二甲基酰胺(DMF)溶液中,150℃下持续搅拌24小时后静置冷却至室温,用饱和食盐水和二氯甲烷萃取,再用无水硫酸镁干燥,过滤,并除去有机溶剂,得到产物粗品,经过层析柱提纯,得到目标产物。
化合物3和4的合成:在氩气保护下,将化合物1或2与4,4′-二甲氧基二苯胺、叔丁醇钾、三(二亚苄基丙酮)二钯、四氟硼酸三叔丁基膦加入邻二甲苯溶液中,105℃下反应20小时后静置冷却至室温,用饱和食盐水和二氯甲烷萃取,再用无水硫酸镁干燥,过滤,并除去有机溶剂,得到产物粗品,经过层析柱提纯,得到目标化合物。
化合物5和6的合成:在氩气保护下,将化合物3或4与联硼酸频那醇酯、乙酸钾、[1,1’-双(二苯基膦基)二茂铁]二氯化钯加入N,N-二甲基甲酰胺溶液中,90℃下反应20小时后静置冷却至室温,用饱和食盐水和二氯甲烷萃取,再用无水硫酸镁干燥,过滤,并除去有机溶剂,得到产物粗品,经过层析柱提纯,得到目标化合物。
(2)聚合物的合成
聚合物I的合成过程:在氩气保护下,将化合物3与化合物5、四(三苯基膦)钯、甲基三辛基氯化铵、加入50mL甲苯和2M碳酸钾水溶液,85℃下持续搅拌20小时。反应结束后,待反应液冷却至室温,将反应混合物在、甲醇溶液中沉淀得到聚合物混合物,加入几滴盐酸与碱进行中和、用丙酮、石油醚、乙酸乙酯和二氯甲烷等溶液进行索氏提取,最后、在、甲醇中再次沉淀,过滤后得到最终产物。
聚合物II的合成过程:合成过程与聚合物I的相似,原料用化合物4与化合物6反应,得到最终产物。
聚合物III的合成过程:合成过程与聚合物I的相似,原料用化合物4与化合物5反应,得到最终产物。
合成路线如下:
(a)1-氟-4-碘苯,碳酸铯,N,N’-二甲基酰胺,150℃,24h.(b)4,4′-二甲氧基二苯胺,叔丁醇钾,三(二亚苄基丙酮)二钯、四氟硼酸三叔丁基膦,邻二甲苯,105℃,20h,N2.(c)联硼酸频那醇酯、乙酸钾、[1,1’-双(二苯基膦基)二茂铁]二氯化钯,N,N-二甲基甲酰胺,90℃,20h,N2.(d)四(三苯基膦)钯、甲基三辛基氯化铵,2M碳酸钾水溶液,甲苯85℃,20h,N2.
一种如权利要求1所述的系列聚咔唑类空穴传输材料的应用,其特征在于这类材料可作为无掺杂的空穴传输材料应用于钙钛矿太阳能电池器件,其中器件结构为ITO玻璃基片/空穴传输层/钙钛矿层/电子传输层/金属电极,其中空穴传输层采用权利要求1所述的系列聚咔唑类空穴传输材料。
本发明的有益效果为:
(1)本发明所述的聚咔唑类空穴传输材料,制备工艺简单、原料易得、价格低廉,非常适宜工业化生产。
(2)本发明所述的聚咔唑类空穴传输材料,玻璃化转变温度较高、热稳定性较好,可以形成很好的无定形膜,有利于提升太阳能电池的环境稳定性。
(3)本发明所述的聚咔唑类空穴传输材料无需掺杂任何添加剂即可以应用于大面积钙钛矿太阳能电池器件中,大面积器件的光电转换效率高于18.6%,说明本发明所述化合物是一类性能优良的空穴传输材料。
附图说明
附图用来提供对本发明的进一步理解,并构成说明书的一部分,与本发明的实例一起用于解释本发明,并不构成对本发明的限制。
图1聚合物I、聚合物II和聚合物III的光电子能谱图;
图2聚合物I、聚合物II和聚合物III的空穴传输性质;
图3聚合物I、聚合物II和聚合物III作为空穴传输材料制成的钙钛矿太阳能电池器件的结构;
图4聚合物I、聚合物II和聚合物III的钙钛矿太阳能电池器件性质图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。此外,下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
实施例1聚合物I的制备;
合成路线如下:
3,6-二溴-9-(4-碘苯基)-9H-咔唑(化合物1)的合成:将150mL圆底烧瓶中,加入3,6-二溴咔唑(5.0g,15mmol),1-氟-4-碘苯(13.5g,60mmol)和碳酸铯(20.0g,60mmol)。然后加入60mL N,N’-二甲基酰胺(DMF),150℃下持续搅拌24小时后静置冷却至室温,用饱和食盐水和二氯甲烷萃取,再用无水硫酸镁干燥,过滤,并除去有机溶剂,得到产物粗品,用二氯甲烷与石油醚溶液体积比为1∶9为流动相进行柱层析纯化粗产物,得到目标产物为白色固体4.05g,产率为52%。1H NMR(400MHz,CDCl3)δ7.94(d,J=8.6Hz,2H),7.51(d,J=8.7Hz,2H),7.24(dd,J=11.5,8.7Hz,6H).13C NMR(101MHz,CDCl3)δ139.71,139.61,139.55,139.50,136.76,129.82,129.72,128.97,128.89,124.30,123.55,123.54,113.61,111.56,111.53,111.49,111.48,93.16.MS:m/z(%)[M+]calcd for C18H10Br2IN:524.82;found:526.002.
3,6-二溴-9-(双[4-甲氧基苯基]-氨基苯基)-9H-咔唑(化合物3)的合成:在氩气保护下,100mL施兰克瓶中,加入化合物(1)(2.8g,5.5mmol),4,4′-二甲氧基二苯胺(1.15g,5.0mmol),叔丁醇钾(1.4g,12.4mmol),三(二亚苄基丙酮)二钯(23mg,0.025mmol),四氟硼酸三叔丁基膦(36mg,0.124mmol)。然后加入50mL邻二甲苯,105℃下持续搅拌20小时后静置冷却至室温,用饱和食盐水和二氯甲烷萃取,再用无水硫酸镁干燥,过滤,并除去有机溶剂,得到产物粗品,用二氯甲烷与石油醚溶液体积比为1∶2为流动相进行柱层析纯化粗产物,得到目标产物为黄色固体1.0g,产率为29%。1H NMR(400MHz,CDCl3)δ7.71(dd,J=5.7,3.3Hz,2H),7.53(dd,J=5.7,3.3Hz,2H),7.50-7.47(m,2H),7.19(dd,J=17.6,8.9Hz,6H),7.05(d,J=8.7Hz,2H),6.89(d,J=9.0Hz,4H),3.82(s,6H).13C NMR(101MHz,CDCl3)δ156.66,148.92,140.49,140.46,129.46,129.36,128.21,127.78,127.72,127.47,127.42,123.86,123.31,120.34,115.16,112.91,111.91,111.83,55.81,55.69.MS:m/z(%)[M+]calcd forC32H24Br2N2O2:626.02;found:626.446.
3,6-双-(4,4,5,5-四甲基-[1,3,2]二氧硼戊环)-9-(双[4-甲氧基苯基]-氨基苯基)-9H-咔唑(化合物5)的合成:根据文献[13],氩气保护下,100mL施兰克瓶中,加入化合物(3)(1.5g,1.6mmol),联硼酸频那醇酯(1.46g,5.76mmol),乙酸钾(0.94g,9.6mmol),[1,1’-双(二苯基膦基)二茂铁]二氯化钯(82mg,0.1mmol)。然后加入30mLN,N-二甲基甲酰胺,90℃下持续搅拌20小时后静置冷却至室温,用饱和食盐水和二氯甲烷萃取,再用无水硫酸镁干燥,过滤,并除去有机溶剂,得到产物粗品,用二氯甲烷与石油醚溶液体积比为1∶2为流动相进行柱层析纯化粗产物,得到目标产物为黄色固体1.63g,产率为39%。1H NMR(400MHz,CDCl3)δ7.71(dd,J=5.7,3.3Hz,1H),7.53(dd,J=5.7,3.3Hz,1H),7.37(d,J=8.2Hz,2H),7.26(s,4H),7.19(d,J=8.9Hz,4H),7.07(d,J=8.9Hz,2H),6.90(d,J=9.0Hz,4H),3.82(s,6H),1.39(s,24H).13C NMR(101MHz,CDCl3)δ156.53,148.57,143.69,140.68,132.37,132.31,129.00,128.26,128.20,127.88,127.81,127.43,127.39,123.22,120.36,115.12,83.79,55.79,55.68,25.20,25.16.MS:m/z(%)[M+]calcd for C44H48B2N2O6:722.37;found:722.709.
聚合物I的合成过程:在氩气保护下,100mL施兰克瓶中,加入化合物3(626mg,1mmol),化合物5(722mg,1mmol),四(三苯基膦)钯(25mg),甲基三辛基氯化铵(三滴)。然后加入50mL甲苯和2M碳酸钾水溶液,85℃下持续搅拌20小时。反应结束后,待反应液冷却至室温,将反应混合物在100mL甲醇溶液中沉淀得到聚合物混合物,加入几滴盐酸与碱进行中和,此时混合物中含有大量的催化剂和盐等杂质。聚合物的后处理过程中分别用丙酮、石油醚、乙酸乙酯和二氯甲烷等溶液进行索氏提取,最后得到二氯甲烷溶液中窄分布、高分子量的聚合物在10mL左右甲醇中再次沉淀,过滤后得到最终产物为灰白色固体。GPC:(Mn=4231,PDI=1.50).1H NMR(300MHz,CDCl3)δ7.71(s,4H),7.56-7.32(m,6H),7.21(d,J=30.9Hz,18H),6.86(s,8H),3.79(d,J=16.9Hz,12H).
实施例2聚合物II的制备;
2,7-二溴-9-(4-碘苯基)-9H-咔唑(化合物2)的合成:合成过程与化合物1的合成过程相似,只是原料用2,7-二溴咔唑(5.0g,15mmol)替代3,6-二溴咔唑,最终粗产物干燥后经过柱层析提纯得到目标产物为黄色固体5.06g,产率为64%。1H NMR(400MHz,CDCl3)δ7.95(dd,J=13.0,7.9Hz,4H),7.41(d,J=8.3Hz,2H),7.27(d,J=6.7Hz,4H).13C NMR(101MHz,CDCl3)δ141.72,139.81,139.77,139.71,136.44,136.39,129.12,129.04,124.25,124.20,124.11,122.04,121.81,121.76,120.36,113.14,113.04,93.56.MS:m/z(%)[M+]calcdfor C18H10Br2IN:524.82;found:557.871.
2,7-二溴-9-(双[4-甲氧基苯基]-氨基苯基)-9H-咔唑(化合物4)的合成:合成过程与化合物3的合成过程相似,只是原料用化合物2(2.8g,5.5mmol)替代化合物1,最终粗产物干燥后经过柱层析提纯得到目标产物为黄色固体1.86g,产率为54%。1H NMR(400MHz,CDCl3)δ7.71(dd,J=5.7,3.3Hz,2H),7.53(dd,J=5.8,3.3Hz,2H),7.48(d,J=1.7Hz,2H),7.20(dd,J=8.9,3.3Hz,6H),7.06(d,J=8.9Hz,2H),6.91(d,J=9.0Hz,4H),3.83(s,6H).13C NMR(101MHz,CDCl3)δ156.71,149.19,142.56,140.45,127.97,127.92,127.70,127.59,127.54,123.52,123.42,121.64,121.59,120.30,120.06,115.19,113.40,113.30,55.81,55.70.MS:m/z(%)[M+]calcd for C32H24Br2N2O2:626.02;found:626.456.
2,7-双-(4,4,5,5-四甲基-[1,3,2]二氧硼戊环)-9-(双[4-甲氧基苯基]-氨基苯基)-9H-咔唑(化合物6)的合成:合成过程与化合物5的合成过程相似,只是原料用化合物4(1.5g,1.6mmol)替代化合物3,最终粗产物干燥后经过柱层析提纯得到目标产物为黄色固体1.67g,产率为40%。1H NMR(400MHz,CDCl3)δ8.15(d,J=7.8Hz,2H),7.73(d,J=7.8Hz,2H),7.27(dd,J=15.8,8.8Hz,8H),7.08(d,J=8.7Hz,2H),6.92(d,J=8.8Hz,4H),3.83(s,6H),1.37(s,24H).13C NMR(101MHz,CDCl3)δ156.52,148.47,141.63,140.80,129.39,128.55,128.49,128.43,127.58,127.52,126.05,125.98,125.53,120.42,120.09,116.59,116.52,115.10,84.02,55.81,55.70,25.14,25.10.MS:m/z(%)[M+]calcd forC44H48B2N2O6:722.37;found:722.768.
聚合物3,6-2,7-PCzTPA的合成过程:合成过程与聚合物3,6-PCzTPA的合成过程相似,只是原料用化合物(4)(626mg,1mmol),化合物(5)(722mg,1mmol),得到最终产物为浅黄色固体。GPC:(Mn=4886,PDI=2.53).1H NMR(300MHz,CDCl3)δ7.68(s,6H),7.36(s,6H),7.21(d,J=30.8Hz,16H),6.90(s,10H),3.71(s,12H).
实施例3聚合物III的制备;
合成路线如下:
化合物1、3、5的合成具体见实施例1,化合物4的合成具体见实施例2;
聚合物II的合成过程:合成过程与聚合物I的合成过程相似,只是原料用化合物4(626mg,1mmol),化合物6(722mg,1mmol),得到最终产物为墨绿色固体。GPC:(Mn=6638,PDI=2.45).1H NMR(300MHz,CDCl3)δ7.71(s,4H),7.56-7.32(m,6H),7.21(d,J=30.9Hz,18H),6.86(s,8H),3.79(d,J=16.9Hz,12H).
实施例4聚合物I、聚合物II和聚合物III的性能表征;
(1)光物理性质的测定;
配制聚合物I、聚合物II和聚合物III的氯苯溶液,使用中国科学院微电子研究所研发的KW-4A型旋涂仪制备化合物的薄膜。采用岛津(Shimadzu)UV-1750紫外可见光谱仪和日立(Hitachi)F-4600荧光光谱仪对化合物的薄膜进行吸收光谱和发射光谱测定。测得薄膜状态下聚合物I、聚合物II和聚合物III的吸收边缘波长(λ)分别为390nm,434nm和414nm,由公式(Eg=1240/λ)计算对应得到其光学带隙(Eg)为3.18eV,2.86eV和3.00eV。
(2)电化学性质的测定;
通过光电子能谱(PESA)测试了聚合物I、聚合物II和聚合物III的HOMO能级分别为-5.22eV、-5.37eV和-5.34eV。
(3)热力学稳定性的测定;
通过热重分析(TGA)和差示扫描量热法(DSC)测试三种空穴传输材料的热性质。聚合物I、聚合物II和聚合物III都具有突出的热稳定性,分解温度为5%时,即Td分别为436℃,422℃和434℃。DSC曲线表明,聚合物I、聚合物II和聚合物III的玻璃相转变温度(Tg)为289℃,261℃和303℃。
(4)电荷迁移率的测定;
化合物的空穴迁移率是用空间电荷限制电流法(SCLC),测试得到聚合物I、聚合物II和聚合物III的迁移率分别为1.46×10-5cm2V-1S-1、1.49×10-6cm2V-1S-1和1.74×10-5cm2V-1S-1。
实施例5聚合物I、聚合物II和聚合物III作为空穴传输材料应用于钙钛矿太阳能电池器件;
将本发明所述的聚合物I、聚合物II和聚合物III作为空穴传输层制备的钙钛矿太阳能电池器件,包括:ITO玻璃基片、钙钛矿层、空穴传输层、电子传输层和金属电极,其中,ITO玻璃基片由玻璃基片和ITO阴极(纳米铟锡金属氧化物玻璃电极)组成,PCBM/C60/BCP作为电子传输层,钙钛矿层作为吸光层,银作为金属电极。
所述钙钛矿太阳能电池器件的制备步骤:
(1)清洗:首先用洗涤剂清洗ITO玻璃基片的表面附着的灰尘等污染物,然后分别用15mL的1%的表面活性剂溶液、水和乙醇超声以除去有机污染物,洗净的ITO玻璃基片用氮气吹干,即可得到实验所需的表面干净的透明导电衬底,再用紫外线-臭氧处理30min,保证其表面干净、清洁;
(2)制备空穴传输层:配制聚合物I、聚合物II和聚合物III的浓度为1mg/mL的氯苯溶液,然后将所配置的溶液以3000rpm的速度旋涂30s沉积到ITO上,100℃退货10分钟;
(3)制备钙钛矿层:由FAI(1M),PbI2(1.1M),MABr(0.2M)和PbBr2(0.22M),CsI(0.065M)混合于DMF∶DMSO=4∶1(v∶v)中得到的1.32M Cs0.05FA0.79MA0.16PbI2.49Br0.51前驱溶液,在空穴传输层上,通过两步旋涂步骤制备钙钛矿层,两步旋涂分别以1000rpm速度转动10s和以6000rpm速度转动20s,在第二次旋涂过程的最后5s中滴加氯苯反溶剂。随后,基片在100℃条件下烘干1h后制得所需钙钛矿层。
(4)制备PCBM层:将50微升10mg/mL的PCBM的氯苯溶液,以1000rpm速度旋涂45s在钙钛矿层上。
(6)置于真空蒸镀室,通过真空蒸镀法将C60(20nm)/BCP(6nm)/银电极(100nm)蒸镀到空穴传输层表面,制得钙钛矿太阳能电池器件。
Claims (3)
1.系列聚咔唑类空穴传输材料,其特征在于,化学结构式如下:
2.一种如权利要求1所述的聚咔唑类空穴传输材料的制备方法,其特征在于,包括如下所述的步骤:
(1)单体合成
化合物1和2的合成:将3,6-二溴咔唑或2,7-二溴咔唑,1-氟-4-碘苯和碳酸铯加入N,N’-二甲基酰胺(DMF)溶液中,150℃下持续搅拌24小时后静置冷却至室温,用饱和食盐水和二氯甲烷萃取,再用无水硫酸镁干燥,过滤,并除去有机溶剂,得到产物粗品,经过层析柱提纯,得到目标产物。
化合物3和4的合成:在氩气保护下,将化合物1或2与4,4′-二甲氧基二苯胺、叔丁醇钾、三(二亚苄基丙酮)二钯、四氟硼酸三叔丁基膦加入邻二甲苯溶液中,105℃下反应20小时后静置冷却至室温,用饱和食盐水和二氯甲烷萃取,再用无水硫酸镁干燥,过滤,并除去有机溶剂,得到产物粗品,经过层析柱提纯,得到目标化合物。
化合物5和6的合成:在氩气保护下,将化合物3或4与联硼酸频那醇酯、乙酸钾、[1,1’-双(二苯基膦基)二茂铁]二氯化钯加入N,N-二甲基甲酰胺溶液中,90℃下反应20小时后静置冷却至室温,用饱和食盐水和二氯甲烷萃取,再用无水硫酸镁干燥,过滤,并除去有机溶剂,得到产物粗品,经过层析柱提纯,得到目标化合物。
(2)聚合物的合成
聚合物I的合成过程:在氩气保护下,将化合物3与化合物5、四(三苯基膦)钯、甲基三辛基氯化铵、加入50mL甲苯和2M碳酸钾水溶液,85℃下持续搅拌20小时。反应结束后,待反应液冷却至室温,将反应混合物在、甲醇溶液中沉淀得到聚合物混合物,加入几滴盐酸与碱进行中和、用丙酮、石油醚、乙酸乙酯和二氯甲烷等溶液进行索氏提取,最后、在、甲醇中再次沉淀,过滤后得到最终产物。
聚合物II的合成过程:合成过程与聚合物I的相似,原料用化合物4与化合物6反应,得到最终产物。
聚合物III的合成过程:合成过程与聚合物I的相似,原料用化合物4与化合物5反应,得到最终产物。
合成路线如下:
(a)1-氟-4-碘苯,碳酸铯,N,N’-二甲基酰胺,150℃,24h.(b)4,4′-二甲氧基二苯胺,叔丁醇钾,三(二亚苄基丙酮)二钯、四氟硼酸三叔丁基膦,邻二甲苯,105℃,20h,N2.(c)联硼酸频那醇酯、乙酸钾、[1,1’-双(二苯基膦基)二茂铁]二氯化钯,N,N-二甲基甲酰胺,90℃,20h,N2.(d)四(三苯基膦)钯、甲基三辛基氯化铵,2M碳酸钾水溶液,甲苯85℃,20h,N2。
3.一种如权利要求1所述的系列聚咔唑类空穴传输材料的应用,其特征在于这类材料可作为无掺杂的空穴传输材料应用于钙钛矿太阳能电池器件,其中器件结构为ITO玻璃基片/空穴传输层/钙钛矿层/电子传输层/金属电极,其中空穴传输层采用权利要求1所述的系列聚咔唑类空穴传输材料。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014202184A1 (en) * | 2013-06-21 | 2014-12-24 | Merck Patent Gmbh | Conjugated polymers |
CN106905169A (zh) * | 2017-01-13 | 2017-06-30 | 中山大学 | 一种乙烯基共轭三芳胺类电荷传输材料及其制备方法 |
CN106957381A (zh) * | 2017-05-12 | 2017-07-18 | 南京工业大学 | 一类钙钛矿太阳能电池的空穴传输材料的设计、合成及应用 |
CN108409636A (zh) * | 2018-03-27 | 2018-08-17 | 南京工业大学 | 一种联咔唑类小分子空穴传输材料的结构、合成及其应用 |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014202184A1 (en) * | 2013-06-21 | 2014-12-24 | Merck Patent Gmbh | Conjugated polymers |
CN106905169A (zh) * | 2017-01-13 | 2017-06-30 | 中山大学 | 一种乙烯基共轭三芳胺类电荷传输材料及其制备方法 |
CN106957381A (zh) * | 2017-05-12 | 2017-07-18 | 南京工业大学 | 一类钙钛矿太阳能电池的空穴传输材料的设计、合成及应用 |
CN108409636A (zh) * | 2018-03-27 | 2018-08-17 | 南京工业大学 | 一种联咔唑类小分子空穴传输材料的结构、合成及其应用 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110970564A (zh) * | 2019-12-23 | 2020-04-07 | 吉林大学 | 一种以TBA-Azo为界面疏水层的钙钛矿太阳能电池及其制备方法 |
CN110970564B (zh) * | 2019-12-23 | 2021-04-13 | 吉林大学 | 一种以TBA-Azo为界面疏水层的钙钛矿太阳能电池及其制备方法 |
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