CN107721906A - 一类新型可溶液加工的9,9-二芳基芴类三聚体空穴传输材料的制备及其在钙钛矿太阳能电池中的应用 - Google Patents
一类新型可溶液加工的9,9-二芳基芴类三聚体空穴传输材料的制备及其在钙钛矿太阳能电池中的应用 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C217/94—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- 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
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
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- H—ELECTRICITY
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- 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
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- 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
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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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
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Abstract
本发明公开了一类新型可溶液加工的可用于钙钛矿太阳能电池空穴传输层的9,9‑二芳基芴类三聚体材料,所述材料的主要结构单元是通过拜耳‑维立格重排和格氏反应制备。本发明所述的空穴传输材料制备工艺简单、原料易得、价格低廉,且材料的溶液加工性能好、空穴迁移率较好,能够大大降低钙钛矿太阳能电池的器件制备成本;这类材料作为非掺杂空穴传输材料应用于钙钛矿太阳电池器件上,实现高于10%的器件效率,适宜于稳定、低成本、大规模柔性钙钛矿太阳能电池器件的制备,是一类具有潜力的钙钛矿太阳能电池空穴传输材料。
Description
技术领域
本发明属于钙钛矿太阳能电池新材料领域,具体地涉及一类9,9-二芳基芴类三聚体空穴传输材料的制备及其在钙钛矿太阳能电池中的应用。
技术背景
近年来,钙钛矿太阳能电池以其较强的吸收、良好电荷迁移率、可溶液化加工等优点吸引了大量研究者的关注。其中,有机-无机卤化物钙钛矿太阳能电池(PSCs)的光电转换效率已经从3.8%迅速增加到22.1%,而且因其成本低廉、光电转换效率高等优势成为当今光伏领域最重要的研究热点之一,并且有可能取代硅成为下一代太阳能电池。钙钛矿太阳能电池的吸光层CH3NH3PbX3(X=Cl、Br、I)具有典型ABX3型立方晶体结构,该结构中A代表有机胺阳离子(如CH3NH3 +等),占据立方八面体的体心;B代表可配位形成八面体的金属阳离子,如Pb+、Nb+、Ti4+、Fe3+等;X代表可与B配位形成八面体的阴离子,可由Cl-、Br-、I-、O2-等构成,该类有机/无机杂化钙钛矿材料中卤素八面体共顶连接,形成稳定的三维网络结构。钙钛矿太阳能电池的器件结构包括电子传输材料(ETMs)和空穴传输材料(HTMs)两层有机传输层,其中HTMs作为钙钛矿晶体和金属电极之间重要的界面层,在促进空穴的提取、传输以及抑制钙钛矿和HTMs界面处的载流子复合等方面起着非常重要的作用,可以显著地提高器件的性能,因而得到了广泛地研究。在倒置结构的钙钛矿天阳能电池中,聚(3,4-乙撑二氧噻吩):聚苯乙烯磺酸盐(PEDOT:PSS)作为常用的空穴传输材料被广泛的使用,但其将强的吸湿性以及酸性对电池性能有较大的负面影响,并且材料制备成本高限制了电池的大面积制备。[3-5]针对目前常用的空穴传输材料PEDOT:PSS合成路线复杂、价格昂贵等问题,科研人员研制了一系列易于合成且成本低廉的小分子作为空穴传输材料。例如咔唑和噻吩类三聚体HTMs、聚三芳胺(PTAAs)等。[1-2]然而大部分所报道的有机HTMs往往需要掺杂4-叔丁基吡啶(t-BP)、有机锂盐(Li-TFSI)和钴的配合物等添加剂来改善其迁移率,从而获得较高的器件性能。这些添加剂不仅使器件的制备过程更加复杂化,而且对PSCs的稳定性和寿命有不目前为止,大部分报道的稳定的HTMs需要多步合成路线和复杂的提纯步骤,成本较高,而且有些材料溶解性差,严重影响其成膜性。因此,有必要进一步开发新的策略、设计低成本、高稳定性的具有较高的电荷迁移率和空穴传输能力的HTMs。
针对以上技术问题,本申请发明人设计合成了一类基于9,9-二芳基芴的三聚体材料。通过拜耳-维立格重排和格氏反应,以2,7-二溴芴酮为原料,在芴的9号位引入两个苯环的同时,并在其4号位引入辛基取代基或9-N-己基咔唑以改善其溶解性能,并通过Suzuki反应与不同化合物进行耦合。该类材料制备简单且具有良好的热稳定性和较好的溶解性能,可以通过溶液法加工,是一种具有潜力的可以广泛应用于PSCs的空穴传输材料。
[1]A.Molina-Ontoria,I.Zimmermann,I Garcia-Benito,P.Gratia,C.Roldán-Carmona,S.Aghazada,M.Graetzel,M.K.Nazeeruddin,and N.Martín.Angew.Chem.Int.Ed.2016,55,6270-6274.
[2]W.S.Yang,J.H Noh,N.J.Jeon,Y.C.Kim,S.Ryu,J.Seo,S.I.Seok,Science.2015,348,1234-1237.
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发明内容
本发明的目的是提供一类新型钙钛矿太阳能电池空穴传输材料的合成及应用。通过采用简单、成本低廉的制备工艺,获得具有良好溶解性、成膜性好,并具有较高空穴迁移率的9,9-二芳基芴类三聚体材料。将其应用于钙钛矿太阳能电池中,可作为空穴传输材料制备较高光电转换效率、空气稳定的钙钛矿太阳能电池。
本发明的新型可溶液加工的可用于钙钛矿太阳能电池空穴传输层的9,9-二芳基芴类三聚体材料,其结构特点在于:芴的9号位是二芳基取代基团,芴的4号位是通过醚键相连的辛基取代基团或9-N-己基咔唑,所述材料结构特征如下:
其中:R为辛基取代基或9-N-己基咔唑,具体为下列结构中的一种:
Ar为三苯胺或9-N苯基咔唑供电子基团,具体为下列结构中的一种:
本发明中所述的一类新型可溶液加工的可用于钙钛矿太阳能电池空穴传输层的9,9-二芳基芴类三聚体的制备方法,其特征在于:主要结构单元与取代基团可通过Suzuki耦合反应制备,具体反应步骤:
其中:R为辛基取代基或9-N-己基咔唑,具体为下列结构中的一种:
Ar为三苯胺或9-N苯基咔唑供电子基团,具体为下列结构中的一种:
将2,7-溴-二芳基芴单体(1equiv)分别与4-硼酸三苯胺(2.5equiv)或9-(4-硼酸频哪醇酯苯基)咔唑(2.5equiv)溶于25mL四氢呋喃为溶剂,然后加入碳酸钾水溶液(2ml,2M),以四三苯基膦钯(70mg)为催化剂,在氮气保护的条件下反应24h制备获得。
本发明所述的该类新型的钙钛矿太阳能电池空穴传输材料,其特征在于可作为空穴传输层应用于钙钛矿太阳能电池,器件结构为ITO/空穴传输层/钙钛矿层/电子传输层/LiF/金属电极Al,其中空穴传输层采用权利要求1所述的9,9-二芳基芴类三聚体材料制成。
本发明中所述的新型9,9-二芳基芴类三聚体材料作为钙钛矿太阳能电池空穴传输层的制备方法,其特征在于该类材料不需要经过退火过程,在手套箱中使溶剂自然挥发,具体步骤如下:将本发明所述材料(10mg)溶于1ml甲苯溶剂中,然后以2000rpm的速度在空气中旋涂40s,将旋好的薄膜放在手套箱中静置2h,待溶剂自然挥发干后,再将配好的钙钛矿溶液旋涂在传输层上。
本发明的有益效果为:
(1)本发明所述的,其制备工艺简单、原料易得、价格低廉,反应条件温和,适宜大规模生产;
(2)本发明所述的一类新型的可应用于钙钛矿太阳能电池空穴传输层的9,9-二芳基芴类三聚体材料,其溶液加工性能好,相对于PEDOT:PSS,其吸湿性差,有利于钙钛矿太阳能电池在空气中的稳定性;
(3)本发明所述的9,9-二芳基芴类三聚体材料,其应用于钙钛矿太阳能电池空穴传输层,较好的高质量薄膜,降低器件制备成本;且可作为非掺杂的空穴传输材料应用于钙钛矿太阳电池器件上,实现高于10%的器件效率,适宜稳定的、低成本、大规模柔性钙钛矿太阳能电池器件应用。
附图说明
图1:本发明所述4种空穴传输材料薄膜的紫外-可见吸收光谱性质图;
图2:本发明所述4种空穴传输材料的TGA曲线图;
图3:本发明所述4种空穴传输材料的循环伏安曲线图;
图4:本发明4种材料作为空穴传输层制成的钙钛矿太阳能电池器件的结构图。
图5:本发明4种材料作为空穴传输层制成的钙钛矿太阳能电池的J-V曲线图。
具体实施方式
实施实例1:MC6Cz-TPA的合成;
取2,7-二溴-4-己基咔唑-9,9-二芳基芴(1.14g,1.6mmol,1equiv)、4-硼酸三苯胺(1.6g,5.4mmol,3.5equiv)溶于25ml干燥鼓泡充满N2的四氢呋喃、10ml碳酸钾水溶液(2mol/L)的混合溶剂中,然后加入80mg钯催化剂四三苯基膦钯,避光充放N2,在85℃下反应24h后用二氯甲烷萃取,之后干燥旋蒸用石油醚∶二氯甲烷=6∶1硅胶柱纯化,得到粉末状固体,产率(53%)
实施实例2:MC8-TPA的合成;
取2,7-二溴-4-辛氧基-9,9-二芳基芴(1g,1.6mmol,1equiv)、4-硼酸三苯胺(1.6g,5.4mmol,3.5equiv)溶于25ml干燥鼓泡充满N2的四氢呋喃、10ml碳酸钾水溶液(2mol/L)的混合溶剂中,然后加入80mg钯催化剂四三苯基膦钯,避光充放N2,在85℃下反应24h后用二氯甲烷萃取,之后干燥旋蒸用石油醚∶二氯甲烷=6∶1硅胶柱纯化,得到粉末状固体,产率(48%)
实施实例3:MC6Cz-9-NPC的合成;
取2,7-二溴-4-己基咔唑-9,9-二芳基芴(1.2g,1.6mmol,1equiv)、9-(4-硼酸频哪醇酯苯基)咔唑(2.4g,6.5mmol,4equiv)溶于25ml干燥鼓泡充满N2的四氢呋喃、10ml碳酸钾水溶液(2mol/L)的混合溶剂中,然后加入80mg钯催化剂四三苯基膦钯,避光充放N2,在85℃下反应24h后用二氯甲烷萃取,之后干燥旋蒸用石油醚∶二氯甲烷=6∶1硅胶柱纯化,得到粉末状固体,产率(56%)
实施实例4:MC8-9-NPC的合成;
取2,7-二溴-4-辛氧基-9,9-二芳基芴(1.2g,2mmol,1equiv)、9-(4-硼酸频哪醇酯苯基)咔唑(3g,8mmol,4equiv)溶于25ml干燥鼓泡充满N2的四氢呋喃、10ml碳酸钾水溶液(2mol/L)的混合溶剂中,然后加入80mg钯催化剂四三苯基膦钯,避光充放N2,在85℃下反应24h后用二氯甲烷萃取,之后干燥旋蒸用石油醚∶二氯甲烷=6∶1硅胶柱纯化,得到粉末状固体,产率(54%)
实施实例5:芴基三聚体材料光物理性质的测定;
a)紫外可见吸收光谱:所有材料的吸收光谱(薄膜)均采用岛津(Shimadzu)UV-3600紫外可见光谱仪进行测定。测试样品配制浓度为1×10-3mol L-1的甲苯溶液,其中,薄膜制备使用的仪器为中国科学院微电子研究所研发的KW-4A型旋涂仪;
a)荧光发射光谱:所有材料的荧光发射光谱(薄膜)测试均采用Hitachi F-4600光谱仪,测试样品配制浓度为1×10-5mol L-1的甲苯溶液,激发波长为紫外可见吸收光谱的最大波长。其中,薄膜制备使用的仪器为中国科学院微电子研究所研发的KW-4A型旋涂仪。
实施实例6:芴基三聚体材料电化学性质的测定;
9,9-二芳基芴类三聚体材料的电化学性质是用电化学循环伏安法(CV)来测定的,实验仪器是辰华CHI660E电化学工作站,该仪器采用的是三电极体系,包括玻碳工作电极、Ag/Cl参比电极以及铂丝对电极。电化学测定使用的溶剂一般为干燥的乙腈,电解质为六氟磷四丁基铵(Bu4NPF6),浓度是0.1M;测试环境需要氮气保护。仪器扫描的速率是0.05V/s,基准物为二茂铁(FOC),分别通过测量氧化和还原过程的开始电压计算该材料的HOMO和LUMO能级。
实施实例7:芴基三聚体材料热力学稳定性的测定;
热重(TGA)测试:TGA图谱测试于Shimadzu DTG-60H热重仪,在氮气保护条件下,升温速率为10℃/min,同时保护气流氮气的流速为40cm3/min,材料重量发生变化直至达到恒重状态。
实施实例8:钙钛矿太阳能电池器件的制备;
将本发明所述的9,9-二芳基芴类三聚体材料作为空穴传输层制备的钙钛矿太阳能电池器件,其结构为:ITO玻璃基片/空穴传输层/钙钛矿层/电子传输层/LiF/金属电极Al,其中空穴传输层采用本发明所述的9,9-二芳基芴类三聚体材料制成,钙钛矿层作为吸光层。
所述钙钛矿太阳能电池器件的制作程序:
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,然后用乙醇和丙酮超声以除去有机污染物,再用超纯水冲洗三次,洗净的ITO玻璃基片用氮气吹干,再用紫外线-臭氧处理30min,保证其表面干净、清洁;
2)空穴传输层的制备:将本发明所述材料(10mg)溶于1ml甲苯溶剂中,然后以2000rpm的速度在空气中旋涂40s,将旋好的薄膜放在手套箱中静置2h,待溶剂自然挥发干后,再将配好的钙钛矿溶液旋涂在传输层上。
3)制备钙钛矿层:分别称取461mgPbI2和159mgCH3NH3I溶于DMSO:DMF(1∶4,v/v),60℃下搅拌1h,然后将共混溶液旋涂在空穴传输层表面(4000rpm,30s),在第二次旋涂前将250μL的氯苯滴在表面淋洗,然后100℃下退火1h,制得所需钙钛矿层。
4)电子传输层的制备:称取18mg富勒烯衍生PC61BM溶于1mL氯苯溶液,60℃下搅拌12h,然后将其用滤头过滤并旋涂在钙钛矿层上(1000rpm,60s)。
5)电极蒸镀:将旋涂好的ITO玻璃片置于真空蒸镀室,通过真空蒸镀法分别将电子传输层LiF(0.8nm)和金属电极Al(100nm)蒸镀在电子传输层表面,制得所需钙钛矿太阳能电池器件。
Claims (4)
1.一类新型可溶液加工的可用于钙钛矿太阳能电池空穴传输层的9,9-二芳基芴类三聚体材料,其结构特点在于:芴的9号位是二芳基取代基团,芴的4号位是通过醚键相连的辛基取代基团或9-N-己基咔唑,所述材料结构特征如下:
其中:R为辛基取代基或9-N-己基咔唑,具体为下列结构中的一种:
Ar为三苯胺或9-N苯基咔唑供电子基团,具体为下列结构中的一种:
2.一种如权利1所述的一类新型可溶液加工的可用于钙钛矿太阳能电池空穴传输层的9,9-二芳基芴类三聚体的制备方法,其特征在于:主要结构单元与取代基团可通过Suzuki耦合反应制备,具体反应步骤:
其中:R为辛基取代基或9-N-己基咔唑,具体为下列结构中的一种:
Ar为三苯胺或9-N苯基咔唑供电子基团,具体为下列结构中的一种:
将2,7-溴-二芳基芴单体(1equiv)分别与4-硼酸三苯胺(2.5equiv)或9-(4-硼酸频哪醇酯苯基)咔唑(2.5equiv)溶于25mL四氢呋喃为溶剂,然后加入碳酸钾水溶液(2ml,2M),以四三苯基膦钯(70mg)为催化剂,在氮气保护的条件下反应24h制备获得。
3.一种如权利1所述的9,9-二芳基芴类三聚体材料应用于钙钛矿太阳能电池器件,其中空穴传输层采用权利要求1所述的9,9-二芳基芴类三聚体材料制成,器件结构为ITO/空穴传输层/钙钛矿层/电子传输层/LiF/金属电极Al。其中空穴传输层采用权利要求1所述的9,9-二芳基芴类三聚体材料制成。
4.一种如权力1所述9,9-二芳基芴类三聚体材料作为钙钛矿太阳能电池空穴传输层的制备方法,其特征在于该类材料不需要经过退火过程,在手套箱中使溶剂自然挥发,具体步骤如下:
将权力1所述材料(10mg)溶于1ml甲苯溶剂中,然后以2000rpm的速度在空气中旋涂40s,将旋好的薄膜放在手套箱中静置2h,待溶剂自然挥发干后,再将配好的钙钛矿溶液旋涂在传输层上。
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CN110518125A (zh) * | 2019-08-01 | 2019-11-29 | 北京科技大学 | 一种阳离子掺杂钙钛矿太阳能电池的制备方法 |
CN113549169A (zh) * | 2021-06-15 | 2021-10-26 | 南京工业大学 | 一种苯基芴胺类聚合物空穴传输材料及其制备方法和应用 |
CN113903862A (zh) * | 2021-09-01 | 2022-01-07 | 苏州大学 | 基于苯硼酸衍生物修饰的SnO2钙钛矿太阳能电池的制备方法 |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110518125A (zh) * | 2019-08-01 | 2019-11-29 | 北京科技大学 | 一种阳离子掺杂钙钛矿太阳能电池的制备方法 |
CN113549169A (zh) * | 2021-06-15 | 2021-10-26 | 南京工业大学 | 一种苯基芴胺类聚合物空穴传输材料及其制备方法和应用 |
CN113903862A (zh) * | 2021-09-01 | 2022-01-07 | 苏州大学 | 基于苯硼酸衍生物修饰的SnO2钙钛矿太阳能电池的制备方法 |
CN113903862B (zh) * | 2021-09-01 | 2023-08-08 | 苏州大学 | 基于苯硼酸衍生物修饰的SnO2钙钛矿太阳能电池的制备方法 |
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