基于芳香族配体的二维钙钛矿太阳能电池研究进展 增强出版

{ "defaultlang": "zh", "titlegroup": { "articletitle": [ { "lang": "zh", "data": [ { "name": "text", "data": "基于芳香族配体的二维钙钛矿太阳能电池研究进展" } ] }, { "lang": "en", "data": [ { "name": "text", "data": "Progress of two-dimensional perovskite solar cells based on the aromatic organic spacers" } ] } ] }, "contribgroup": { "author": [ { "name": [ { "lang": "zh", "surname": "高玉", "givenname": "平", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "GAO", "givenname": "Yu-ping", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "" } ], "role": [ "first-author" ], "bio": [ { "lang": "zh", "text": [ "高玉平（1995－），男，河南信阳人，在读博士，2021年于中国科学技术大学获得硕士学位，2021年至今就读于南开大学化学学院，研究方向为钙钛矿太阳能电池。E-mail： ypgao@nankai.mail.edu.cn。" ], "graphic": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124014&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124016&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124015&type=", "width": "27.16399956", "height": "38.11799622", "fontsize": "" } ], "data": [ [ { "name": "text", "data": "高玉平" }, { "name": "text", "data": "（1995－），男，河南信阳人，在读博士，2021年于中国科学技术大学获得硕士学位，2021年至今就读于南开大学化学学院，研究方向为钙钛矿太阳能电池。E-mail： " }, { "name": "text", "data": "ypgao@nankai.mail.edu.cn" }, { "name": "text", "data": "。" } ] ] } ], "email": "ypgao@nankai.mail.edu.cn", "deceased": false }, { "name": [ { "lang": "zh", "surname": "王", "givenname": "瑞", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "WANG", "givenname": "Rui", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "" } ], "role": [], "deceased": false }, { "name": [ { "lang": "zh", "surname": "刘", "givenname": "永胜", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "LIU", "givenname": "Yong-sheng", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "" } ], "role": [ "corresp" ], "corresp": [ { "rid": "cor1", "lang": "en", "text": "LIU Yong-sheng， E-mail： Liuys@nankai.edu.cn", "data": [ { "name": "text", "data": "LIU Yong-sheng， E-mail： Liuys@nankai.edu.cn" } ] } ], "bio": [ { "lang": "zh", "text": [ "刘永胜 （1978－），男，山西怀仁人，教授，博士生导师，2009年于南开大学获得博士学位，主要从事有机及有机无机杂化半导体材料和光伏器件的研究。E-mail： liuys@nankai.edu.cn。" ], "graphic": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124017&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124019&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124018&type=", "width": "28.18700027", "height": "40.37500000", "fontsize": "" } ], "data": [ [ { "name": "text", "data": "刘永胜" }, { "name": "text", "data": " （1978－），男，山西怀仁人，教授，博士生导师，2009年于南开大学获得博士学位，主要从事有机及有机无机杂化半导体材料和光伏器件的研究。E-mail： " }, { "name": "text", "data": "liuys@nankai.edu.cn" }, { "name": "text", "data": "。" } ] ] } ], "email": "liuys@nankai.edu.cn", "deceased": false } ], "aff": [ { "id": "aff1", "intro": [ { "lang": "zh", "text": "南开大学化学学院，高分子化学研究所，天津　300071", "data": [ { "name": "text", "data": "南开大学化学学院，高分子化学研究所，天津　300071" } ] }, { "lang": "en", "text": "Institute of Polymer Chemistry， College of Chemistry， Nankai University， Tianjin 300071， China", "data": [ { "name": "text", "data": "Institute of Polymer Chemistry， College of Chemistry， Nankai University， Tianjin 300071， China" } ] } ] } ] }, "abstracts": [ { "lang": "zh", "data": [ { "name": "p", "data": [ { "name": "text", "data": "近年来，钙钛矿太阳能电池（PSCs）的效率得到了快速的发展，目前已经获得25.7%的认证效率，可与硅基太阳能电池相媲美。然而，PSCs的稳定性却远不如硅基太阳能电池，这限制了PSCs的使用。与此同时，二维（2D）或准二维钙钛矿材料得到了越来越多的关注，主要是因为大体积有机配体的引入明显地改善了材料的结构和环境稳定性。在2D PSCs领域，有机配体离子的设计和选择会直接影响材料的光电性能和器件的效率。目前2D PSCs中所使用的有机配体主要分为：脂肪族配体和芳香族配体。芳香族配体由于具有较大的介电常数、改善的电荷传输和可调控的组装结构等优点得到越来越多的关注。本文系统地总结了芳香族配体材料对2D钙钛矿性能的影响，以及其在2D PSCs领域的应用。" } ] } ] }, { "lang": "en", "data": [ { "name": "p", "data": [ { "name": "text", "data": "Perovskite solar cells （PSCs） have undergone unprecedented rapid development in the past decade. A certified power conversion efficiency （PCE） of 25.7% has been achieved， which is comparable to that of commercialized silicon solar cells. However， the inferior stability under heat and moisture has hindered their commercial application. Two-dimensional （2D） or quasi-2D perovskite materials have attracted considerable interest due to their superior structural and environmental stability in comparison with their 3D counterpart. The organic spacers play a very important role in 2D perovskites and they could directly affect the optoelectronic properties of the materials and the PCE of the devices. The organic spacers for 2D PSCs mainly include aliphatic spacers and aromatic spacers. The aromatic spacers have received more and more attention because of their large dielectric constants， superior charge transport properties and tunable self-assembly structures. In this review， we systematically summarize the effects of aromatic spacers on the structural and optoelectronic properties of 2D perovskite materials， and their applications in 2D PSCs." } ] } ] } ], "keyword": [ { "lang": "zh", "data": [ [ { "name": "text", "data": "二维钙钛矿" } ], [ { "name": "text", "data": "太阳能电池" } ], [ { "name": "text", "data": "稳定性" } ], [ { "name": "text", "data": "电荷传输" } ] ] }, { "lang": "en", "data": [ [ { "name": "text", "data": "two-dimensional perovskite" } ], [ { "name": "text", "data": "solar cell" } ], [ { "name": "text", "data": "stability" } ], [ { "name": "text", "data": "charge transport" } ] ] } ], "highlights": [], "body": [ { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "1　引　　言" } ], "level": "1", "id": "s1" } }, { "name": "p", "data": [ { "name": "text", "data": "近十年来，钙钛矿材料由于具有较高的载流子迁移率、较长的载流子寿命和扩散长度以及较低的缺陷密度等优点获得了各国科研人员的广泛关注" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "1", "type": "bibr", "rid": "R1", "data": [ { "name": "text", "data": "1" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "2", "type": "bibr", "rid": "R2", "data": [ { "name": "text", "data": "2" } ] } } ], "rid": [ "R1", "R2" ], "text": "1-2", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。目前钙钛矿材料已经被广泛地应用于太阳能电池（PSCs）" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "3", "type": "bibr", "rid": "R3", "data": [ { "name": "text", "data": "3" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "4", "type": "bibr", "rid": "R4", "data": [ { "name": "text", "data": "4" } ] } } ], "rid": [ "R3", "R4" ], "text": "3-4", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、发光二极管" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "5", "type": "bibr", "rid": "R5", "data": [ { "name": "text", "data": "5" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "7", "type": "bibr", "rid": "R7", "data": [ { "name": "text", "data": "7" } ] } } ], "rid": [ "R5", "R6", "R7" ], "text": "5-7", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、场效应晶体管" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "8", "type": "bibr", "rid": "R8", "data": [ { "name": "text", "data": "8" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、激光器" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "9", "type": "bibr", "rid": "R9", "data": [ { "name": "text", "data": "9" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "和光探测器" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "10", "type": "bibr", "rid": "R10", "data": [ { "name": "text", "data": "10" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "12", "type": "bibr", "rid": "R12", "data": [ { "name": "text", "data": "12" } ] } } ], "rid": [ "R10", "R11", "R12" ], "text": "10-12", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "等领域。其中，在太阳能电池领域，钙钛矿材料的应用和研究最为广泛。2009年，Miyasaka教授首次报道了基于钙钛矿材料构建的太阳能电池，并获得了3.8%的能量转化效率（PCE）" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "R13", "data": [ { "name": "text", "data": "13" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。并且，在接下来的短短十年中，钙钛矿太阳能电池（PSCs）的PCE已经获得了25.7%的认证效率" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "14", "type": "bibr", "rid": "R14", "data": [ { "name": "text", "data": "14" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，该值可与商业化的晶硅太阳能电池相媲美。然而，钙钛矿太阳能电池的稳定性依旧没有得到实质性的改善" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "15", "type": "bibr", "rid": "R15", "data": [ { "name": "text", "data": "15" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，这已经成为PSCs商业化应用的主要障碍。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "为了克服稳定性的问题，研究人员采取了一系列措施，包括界面工程" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "14", "type": "bibr", "rid": "R14", "data": [ { "name": "text", "data": "14" } ] } }, { "name": "text", "data": ", " }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "16", "type": "bibr", "rid": "R16", "data": [ { "name": "text", "data": "16" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "20", "type": "bibr", "rid": "R20", "data": [ { "name": "text", "data": "20" } ] } } ], "rid": [ "R16", "R17", "R18", "R19", "R20" ], "text": "16-20", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、缺陷工程" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "21", "type": "bibr", "rid": "R21", "data": [ { "name": "text", "data": "21" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "22", "type": "bibr", "rid": "R22", "data": [ { "name": "text", "data": "22" } ] } } ], "rid": [ "R21", "R22" ], "text": "21-22", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、掺杂处理" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "20", "type": "bibr", "rid": "R20", "data": [ { "name": "text", "data": "20" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "21", "type": "bibr", "rid": "R21", "data": [ { "name": "text", "data": "21" } ] } } ], "rid": [ "R20", "R21" ], "text": "20-21", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、全无机钙钛矿" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "25", "type": "bibr", "rid": "R25", "data": [ { "name": "text", "data": "25" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "26", "type": "bibr", "rid": "R26", "data": [ { "name": "text", "data": "26" } ] } } ], "rid": [ "R25", "R26" ], "text": "25-26", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、和封装技术" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "27", "type": "bibr", "rid": "R27", "data": [ { "name": "text", "data": "27" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "等。然而目前三维（3D）钙钛矿材料和器件的稳定性仍然没有达到商业化需求。提高钙钛矿材料本征稳定性有效的方法是将大体积有机配体引入到3D钙钛矿材料中，使其沿着某一特定的轴剪切成二维（2D）材料或者准2D材料" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "28", "type": "bibr", "rid": "R28", "data": [ { "name": "text", "data": "28" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "30", "type": "bibr", "rid": "R30", "data": [ { "name": "text", "data": "30" } ] } } ], "rid": [ "R28", "R29", "R30" ], "text": "28-30", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。大尺寸有机阳离子具有较高的热稳定性及优异的疏水性，用其形成的二维钙钛矿具有较大的形成能，因此（准）2D PSC在理论和实际上均具有更优异的稳定性。虽然目前所报道的准2D PSCs的最高效率已经超过了22%" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "31", "type": "bibr", "rid": "R31", "data": [ { "name": "text", "data": "31" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，但仍滞后于3D PSCs的效率。这主要归因于二维钙钛矿多量子阱结构导致的介电和量子限域效应。具体来说，在2D钙钛矿材料中，有机层的介电常数远低于无机钙钛矿层，这种现象所产生的强介电限域效应增大了2D钙钛矿的激子结合能（E" }, { "name": "sub", "data": [ { "name": "text", "data": "b" } ] }, { "name": "text", "data": "），同时也导致了2D钙钛矿层与层之间电荷传输能力的下降，从而降低了器件效率" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "32", "type": "bibr", "rid": "R32", "data": [ { "name": "text", "data": "32" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。另一方面，2D钙钛矿具有天然的多量子阱结构" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "33", "type": "bibr", "rid": "R33", "data": [ { "name": "text", "data": "33" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "35", "type": "bibr", "rid": "R35", "data": [ { "name": "text", "data": "35" } ] } } ], "rid": [ "R33", "R34", "R35" ], "text": "33-35", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，钙钛矿层充当潜在的“阱”，有机层充当潜在的“势垒”。这种量子限域效应也导致了2D钙钛矿材料激子结合能的增加。同时，光生载流子被限制在量子阱中，进一步降低了材料的电荷传输能力。因此，合理的选择和设计有机配体是提高2D PSCs效率的关键" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "36", "type": "bibr", "rid": "R36", "data": [ { "name": "text", "data": "36" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "38", "type": "bibr", "rid": "R38", "data": [ { "name": "text", "data": "38" } ] } } ], "rid": [ "R36", "R37", "R38" ], "text": "36-38", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2D钙钛矿器件中所使用的有机配体主要分为两大类：脂肪族配体和芳香族配体。这两类有机分子在化学结构和物理性质上有着本质的区别，这种差异将进一步影响2D PSCs的晶体结构（无机八面体畸变、层间距等）、光电性质（带隙、激子结合能等）和薄膜质量（晶粒尺寸、结晶度、取向、稳定性等）。相比于脂肪族分子，芳香族有机阳离子配体主要具有以下优点" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "39", "type": "bibr", "rid": "R39", "data": [ { "name": "text", "data": "39" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "：1、芳香族化合物拥有共轭的π电子结构，这使得其具有更高的介电常数，从而降低有机层与无机层的介电失配，更有利于电荷的传输。2、在共轭体系中，电子密度发生了平均化，导致共轭结构的能量降低。因此，芳香族化合物具有更高的稳定性。3、与柔性脂肪族分子的单一组装形式相比，芳香族化合物一般具有刚性平面结构和π-π、CH‧‧‧π相互作用等多种非共价键相互作用和丰富的组装形式" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "38", "type": "bibr", "rid": "R38", "data": [ { "name": "text", "data": "38" } ] } }, { "name": "text", "data": ", " }, { "name": "xref", "data": { "text": "40", "type": "bibr", "rid": "R40", "data": [ { "name": "text", "data": "40" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，这有利于调节晶体的排列和取向。4、由于共轭结构的存在，芳香族分子具有红移的吸收光谱，在可见光范围内可吸收更多的光子。而脂肪族分子的吸收光谱一般位于300 nm以下，这不利于2D PSCs效率的提升。目前，人们广泛探究了各种芳香族配体及其独特的性质（包括共轭环长度、杂原子类型和相互作用等)对准二维钙钛矿的结构和成膜特性的影响。因此，综述芳香族配体的种类、组成和性质，可为制备高性能准二维PSCs提供指导和帮助。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "鉴于此，本综述将系统地总结目前2D PSCs领域使用最广泛的几类芳香族配体，包括苯基衍生物、噻吩基衍生物和杂化、稠环类化合物等。同时比较了不同芳香族配体的结构对2D PSCs光电性能和环境稳定性的影响。最后，我们对高效、稳定的准二维钙钛矿太阳能电池的结构设计、有机配体的定制和内在物理性能优化进行了总结，并简要介绍了未来芳香族分子在2D钙钛矿领域的发展方向。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2　二维钙钛矿的化学和晶体结构" } ], "level": "1", "id": "s2" } }, { "name": "p", "data": [ { "name": "text", "data": "如" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "a所示，钙钛矿的通式可用ABX" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "表示，其中A和B为阳离子，X代表阴离子。B阳离子的配位数为6，一个B阳离子与6个X阴离子相互配位，形成[BX" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "]" }, { "name": "sup", "data": [ { "name": "text", "data": "4-" } ] }, { "name": "text", "data": "正八面体，B占据正八面体中心位置，八面体之间通过角共享形成三维有序结构" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "41", "type": "bibr", "rid": "R41", "data": [ { "name": "text", "data": "41" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。一个A阳离子与12个X阴离子配位形成［AX" }, { "name": "sub", "data": [ { "name": "text", "data": "12" } ] }, { "name": "text", "data": "］立方八面体，A占据立方八面体的中心位置。在PSCs领域，A位阳离子通常为半径较大的阳离子，例如甲胺阳离子（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "NH" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": ",MA" }, { "name": "sup", "data": [ { "name": "text", "data": "+" } ] }, { "name": "text", "data": "）、甲脒阳离子（CH" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "NH=CH" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": ",FA" }, { "name": "sup", "data": [ { "name": "text", "data": "+" } ] }, { "name": "text", "data": "）或者Cs" }, { "name": "sup", "data": [ { "name": "text", "data": "+" } ] }, { "name": "text", "data": "、Ru" }, { "name": "sup", "data": [ { "name": "text", "data": "+" } ] }, { "name": "text", "data": "等；B位阳离子通常为半径较小的二价离子，如Pb" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "或Sn" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "；X位阴离子通常为卤素离子，如I" }, { "name": "sup", "data": [ { "name": "text", "data": "-" } ] }, { "name": "text", "data": "，Br" }, { "name": "sup", "data": [ { "name": "text", "data": "-" } ] }, { "name": "text", "data": "，Cl" }, { "name": "sup", "data": [ { "name": "text", "data": "-" } ] }, { "name": "text", "data": "等。2D钙钛矿通常被认为是将3D钙钛矿沿着" }, { "name": "text", "data": "<" }, { "name": "text", "data": "110" }, { "name": "text", "data": ">" }, { "name": "text", "data": "，" }, { "name": "text", "data": "<" }, { "name": "text", "data": "111" }, { "name": "text", "data": ">" }, { "name": "text", "data": "和" }, { "name": "text", "data": "<" }, { "name": "text", "data": "100" }, { "name": "text", "data": ">" }, { "name": "text", "data": "晶面切割而来（" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "b）" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "42", "type": "bibr", "rid": "R42", "data": [ { "name": "text", "data": "42" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。因此，按照不同的剪切面对其进行分类可相应得到三种不同取向的2D钙钛矿家族：" }, { "name": "text", "data": "<" }, { "name": "text", "data": "110" }, { "name": "text", "data": ">" }, { "name": "text", "data": "，" }, { "name": "text", "data": "<" }, { "name": "text", "data": "111" }, { "name": "text", "data": ">" }, { "name": "text", "data": "和" }, { "name": "text", "data": "<" }, { "name": "text", "data": "100" }, { "name": "text", "data": ">" }, { "name": "text", "data": "取向钙钛矿。其中" }, { "name": "text", "data": "<" }, { "name": "text", "data": "100" }, { "name": "text", "data": ">" }, { "name": "text", "data": "取向的2D钙钛矿是迄今为止最常见且应用最为广泛的一类。PSCs领域的2D钙钛矿材料通常为" }, { "name": "text", "data": "<" }, { "name": "text", "data": "100" }, { "name": "text", "data": ">" }, { "name": "text", "data": "取向。" } ] }, { "name": "fig", "data": { "id": "F1", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图1" } ], "title": [ { "name": "text", "data": "（a）ABX" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "钙钛矿结构示意图" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "49", "type": "bibr", "rid": "R49", "data": [ { "name": "text", "data": "49" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。（b）" }, { "name": "text", "data": "<" }, { "name": "text", "data": "100" }, { "name": "text", "data": ">" }, { "name": "text", "data": "、" }, { "name": "text", "data": "<" }, { "name": "text", "data": "110" }, { "name": "text", "data": ">" }, { "name": "text", "data": "和" }, { "name": "text", "data": "<" }, { "name": "text", "data": "111" }, { "name": "text", "data": ">" }, { "name": "text", "data": "平面钙钛矿结构示意图。沿着以上三个方向剪切，形成2D钙钛矿" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "50", "type": "bibr", "rid": "R50", "data": [ { "name": "text", "data": "50" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。（c）3D钙钛矿向2D钙钛矿转变示意图" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "50", "type": "bibr", "rid": "R50", "data": [ { "name": "text", "data": "50" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。（d）RP、DJ、ACI型2D钙钛矿结构对比" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "45", "type": "bibr", "rid": "R45", "data": [ { "name": "text", "data": "45" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.1" } ], "title": [ { "name": "text", "data": "（a） ABX" }, { "name": "sub", "data": [ { "name": "text", "data": "3 " } ] }, { "name": "text", "data": "perovskite structure" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "49", "type": "bibr", "rid": "R49", "data": [ { "name": "text", "data": "49" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": ". （b） Schematic of different oriented families of 2D perovskites： " }, { "name": "text", "data": "<" }, { "name": "text", "data": "100" }, { "name": "text", "data": ">" }, { "name": "text", "data": "， " }, { "name": "text", "data": "<" }, { "name": "text", "data": "110" }, { "name": "text", "data": ">" }, { "name": "text", "data": " and " }, { "name": "text", "data": "<" }, { "name": "text", "data": "111" }, { "name": "text", "data": ">" }, { "name": "text", "data": " plane. Cuts along " }, { "name": "text", "data": "<" }, { "name": "text", "data": "100" }, { "name": "text", "data": ">" }, { "name": "text", "data": "， " }, { "name": "text", "data": "<" }, { "name": "text", "data": "110" }, { "name": "text", "data": ">" }, { "name": "text", "data": " and " }, { "name": "text", "data": "<" }, { "name": "text", "data": "111" }, { "name": "text", "data": ">" }, { "name": "text", "data": " directions （grey parts） result in the corresponding different types of 2D perovskites" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "50", "type": "bibr", "rid": "R50", "data": [ { "name": "text", "data": "50" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": ". （c） Crystal structures of a 3Dperovskite and of the 2D hybrid perovskite with monovalent and divalent ammonium cations" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "50", "type": "bibr", "rid": "R50", "data": [ { "name": "text", "data": "50" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": ". （d） Structural comparison between RP， DJ， and ACI phases" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "45", "type": "bibr", "rid": "R45", "data": [ { "name": "text", "data": "45" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124020&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124022&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124021&type=", "width": "108.95500183", "height": "100.10099792", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "将3D钙钛矿剪切成2D材料的方法是引入体积较大的有机配体，如苯乙胺、噻吩甲胺等。采用这种方法可获得化学结构式为R" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "A" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n-1" } ] } ] }, { "name": "text", "data": "B" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "X" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "3n+1" } ] } ] }, { "name": "text", "data": "、R′A" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n-1" } ] } ] }, { "name": "text", "data": "B" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "X" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n+1" } ] } ] }, { "name": "text", "data": "或者A′A" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "B" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "X" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "3n+1" } ] } ] }, { "name": "text", "data": "的2D或准2D钙钛矿材料（图" }, { "name": "xref", "data": { "text": "1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "1" } ] } }, { "name": "text", "data": "c和" }, { "name": "xref", "data": { "text": "1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "1" } ] } }, { "name": "text", "data": "d）。这三种化学结构式对应着2D 钙钛矿的三种类型，分别为Ruddlesden-Popper（RP型）" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "43", "type": "bibr", "rid": "R43", "data": [ { "name": "text", "data": "43" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、Dion-Jacobson（DJ型）" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "44", "type": "bibr", "rid": "R44", "data": [ { "name": "text", "data": "44" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "45", "type": "bibr", "rid": "R45", "data": [ { "name": "text", "data": "45" } ] } } ], "rid": [ "R44", "R45" ], "text": "44-45", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "以及 Alternating-Cation-Interlayer （ACI型）phases" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "46", "type": "bibr", "rid": "R46", "data": [ { "name": "text", "data": "46" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。以上化学式中R为体积较大的单胺有机阳离子；R′为双胺有机阳离子；A′通常为胍基阳离子（GA" }, { "name": "sup", "data": [ { "name": "text", "data": "+" } ] }, { "name": "text", "data": "）。n值代表着相邻有机层之间无机八面体[BX" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "]" }, { "name": "sup", "data": [ { "name": "text", "data": "4-" } ] }, { "name": "text", "data": "的层数。RP型2D钙钛矿通常由单胺有机配体构建，两个单胺分子“尾-尾”相交，错开排列于无机层之间（如" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "c）。这种堆积结构无法避免范德华间隙的存在。DJ型2D钙钛矿由于引入双胺有机配体，有机分子中的两个氨基分别与无机层相互作用。这种结构具有更短的无机层间距，且避免了范德华间隙的存在，因此理论上更有利于提升结构稳定性和电荷传输。然而，目前DJ型二维钙钛矿的研究相对较少。ACI型2D钙钛矿结构如" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "d所示，该类型的2D钙钛矿通常只设计到胍基有机配体，且相关研究较少，因此本文不对ACI型2D钙钛矿展开论述。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "当二维钙钛矿结构通式中的n趋近于无穷大时（n=∞），形成的是3D钙钛矿；而当n=1时，形成的便是纯2D钙钛矿；当1＜n≤5时，形成的是准2D钙钛矿（为方便叙述，下文中提到的2D钙钛矿通常指的是1＜n≤5的准2D钙钛矿）。随着n值的增加，不同n值之间的热力学稳定性差异变小，使得高n值纯相钙钛矿的形成变得困难。所以，在准二维钙钛矿中往往同时存在低n值相（n=1, 2, 3, 4, 5）和类三维相（n=∞）。另外，n值为1和2的2D PSCs倾向于平行于基底生长，而n＞3的2D PSCs往往垂直于基底生长，垂直于基底生长的钙钛矿具有更优异的电荷传输性能。因此，薄膜取向和相分布对于获得高性能PSCs尤为重要" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "47", "type": "bibr", "rid": "R47", "data": [ { "name": "text", "data": "47" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "48", "type": "bibr", "rid": "R48", "data": [ { "name": "text", "data": "48" } ] } } ], "rid": [ "R47", "R48" ], "text": "47-48", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。具有高介电常数芳香族配体的引入可降低有机层与无机层的介电失配，提高电荷传输效率，改善二维钙钛矿的结构和性能。因此，相比于脂肪族化合物，芳香族配体在制备高效、稳定的准2D PSCs方面具有巨大的潜力。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3　芳香族配体在2D PSCs领域的应用" } ], "level": "1", "id": "s3" } }, { "name": "p", "data": [ { "name": "text", "data": "基于二维钙钛矿的研究现状，我们将芳香族配体分为三大类，并阐明芳香环中烷基链的长度，杂原子的种类、位置和数量，共轭环以及-NH" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "的数量等对钙钛矿结构，薄膜质量（结晶度、取向、相分布等）和光学性能等方面的影响，为新型有机配体的设计提供参考。如" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "所示，目前较为常用的芳香族配体主要为苯基和噻吩基衍生物。" } ] }, { "name": "fig", "data": { "id": "F2", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图2" } ], "title": [ { "name": "text", "data": "用于构建2D PSCs的芳香族配体。（a）苯基有机配体、（b）噻吩基有机配体和（c）其他有机配体分子结构。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.2" } ], "title": [ { "name": "text", "data": "Organic spacers for 2D perovskite solar cells. （a） molecular structure of phenyl organic ligand， （b） thiophenyl organic ligand and （c） other organic ligand." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124023&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124025&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124024&type=", "width": "127.56400299", "height": "71.12000275", "fontsize": "" } ] } }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.1　苯基有机配体在2D PSCs领域的应用" } ], "level": "2", "id": "s3a" } }, { "name": "p", "data": [ { "name": "text", "data": "由于合适的体积和容易修饰等特点，苯环已经成为2D PSCs领域最为常用的芳香族基团。通过在苯环上进行修饰或者延长烷基链长度等手段，研究者可以可控地改变苯基配体的堆积结构。其中，苯乙胺（PEA）及其衍生物是最早被系统研究的芳香族配体。2016年，Kamminga等人首次系统地研究了苯基配体中脂肪链的长度对低维钙钛矿晶体结构的影响" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "36", "type": "bibr", "rid": "R36", "data": [ { "name": "text", "data": "36" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。作者将脂肪链的长度从一个碳原子延长至四个碳原子，分别得到了苯甲铵（PMA）、苯乙铵（PEA）、苯丙铵（PPA）和苯丁铵（PBA）四个配体材料。研究表明，如" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "a所示，PMA和PEA作有机配体时，2D钙钛矿中[PbI" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "]" }, { "name": "sup", "data": [ { "name": "text", "data": "4-" } ] }, { "name": "text", "data": "八面体为正常的角共享结构，而延长烷基链后，PPA和PBA基2D钙钛矿中出现面共享和边共享结构，同时Pb-I-Pb键角增大，晶体结构更加扭曲。这种结构显著降低了材料的电荷传输能力。因此PPA和PBA不适合作为2D钙钛矿的有机配体。Rodríguez-Romero等人对比了苯胺碘盐（PAI）基和丁胺碘盐（BAI）基2D PSCs器件的性能，器件结构为：(PAI)" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "(MAI)" }, { "name": "sub", "data": [ { "name": "text", "data": "n-1" } ] }, { "name": "text", "data": "(PbI" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": ")" }, { "name": "sub", "data": [ { "name": "text", "data": "n" } ] }, { "name": "text", "data": "（表示为AnyIPb" }, { "name": "sub", "data": [ { "name": "text", "data": "n" } ] }, { "name": "text", "data": "）和(BANH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "I)" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "(MAI)" }, { "name": "sub", "data": [ { "name": "text", "data": "n-1" } ] }, { "name": "text", "data": "(PbI" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": ")" }, { "name": "sub", "data": [ { "name": "text", "data": "n" } ] }, { "name": "text", "data": "（表示为BAIPb" }, { "name": "sub", "data": [ { "name": "text", "data": "n" } ] }, { "name": "text", "data": "）" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "51", "type": "bibr", "rid": "R51", "data": [ { "name": "text", "data": "51" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。研究表明，引入极化的π电子体系削弱了2D钙钛矿中有机层和无机层之间的介电限域效应，从而降低了激子结合能，改善了电荷传输。其结果为AnyIPb" }, { "name": "sub", "data": [ { "name": "text", "data": "n" } ] }, { "name": "text", "data": "体系获得了更高的电流和PCE（" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "b）。Xi等人在苯乙胺中引入不饱和的烯基，合成了3-苯基-2-丙烯基胺（PPEA），并将其作为有机配体用于2D钙钛矿材料中，获得了最高14.76%的PCE" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "52", "type": "bibr", "rid": "R52", "data": [ { "name": "text", "data": "52" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。与PEA不同的是，PPEA分子中含有不饱和的烯烃。烯烃上以及末端亚甲基上的氢原子均与无机层末端的碘原子存在强氢键作用（" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "c）。这种额外的多重氢键导致PPEA分子末端的氨基更深地插入无机层的沟壑中，从而促进了晶体垂直方向的生长，增强了2D钙钛矿面外电荷传输能力。同时，这种分子结构上的变化改善了2D钙钛矿(PPEA)" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "(FA" }, { "name": "sub", "data": [ { "name": "text", "data": "0.5" } ] }, { "name": "text", "data": "MA" }, { "name": "sub", "data": [ { "name": "text", "data": "0.5" } ] }, { "name": "text", "data": ")" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "Pb" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n-1" } ] } ] }, { "name": "text", "data": "I" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "3n+1" } ] } ] }, { "name": "text", "data": "(n=2, 3)的相分布，促进了大n值相的生成。Ran等人将PPEA用于Sn基2D钙钛矿中，同样获得了优异的器件性能和稳定性" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "53", "type": "bibr", "rid": "R53", "data": [ { "name": "text", "data": "53" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。在这项研究中，作者发现PPA可调节相分布，促进3D相的生成。此外，PPEA的存在可增大晶粒尺寸（" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "d），诱导垂直晶体取向，促进电荷提取，并增强FASnI" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "薄膜的稳定性。" } ] }, { "name": "fig", "data": { "id": "F3", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图3（a）" } ], "title": [ { "name": "text", "data": "2D钙钛矿结构（n=1）的多面体模型，沿［100］方向投影" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "36", "type": "bibr", "rid": "R36", "data": [ { "name": "text", "data": "36" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。（b）AnyIPb" }, { "name": "sub", "data": [ { "name": "text", "data": "n" } ] }, { "name": "text", "data": "和BAIPb" }, { "name": "sub", "data": [ { "name": "text", "data": "n" } ] }, { "name": "text", "data": "最优器件的J-V曲线" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "51", "type": "bibr", "rid": "R51", "data": [ { "name": "text", "data": "51" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。（c）（PPEA）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "（FA" }, { "name": "sub", "data": [ { "name": "text", "data": "0.5" } ] }, { "name": "text", "data": "MA" }, { "name": "sub", "data": [ { "name": "text", "data": "0.5" } ] }, { "name": "text", "data": "）" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n-1" } ] } ] }, { "name": "text", "data": "Pb" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "I" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "3n+1" } ] } ] }, { "name": "text", "data": "（n=2和3）材料的部分单晶结构" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "52", "type": "bibr", "rid": "R52", "data": [ { "name": "text", "data": "52" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。（d）PPEA" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "FA" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "1-x" } ] } ] }, { "name": "text", "data": "SnI" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "薄膜的晶体尺寸随着PPEA含量的变化关系图" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "53", "type": "bibr", "rid": "R53", "data": [ { "name": "text", "data": "53" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.3" } ], "title": [ { "name": "text", "data": "（a） Polyhedral model of three structural motifs， projected along the ［100］ direction" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "36", "type": "bibr", "rid": "R36", "data": [ { "name": "text", "data": "36" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": ". （b） J-V curves of champion devices prepared with a） AnyIPbn and b） BAIPbn" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "51", "type": "bibr", "rid": "R51", "data": [ { "name": "text", "data": "51" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": ". （c） Part of the single crystal structures of the （PPEA）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "（FA" }, { "name": "sub", "data": [ { "name": "text", "data": "0.5" } ] }, { "name": "text", "data": "MA" }, { "name": "sub", "data": [ { "name": "text", "data": "0.5" } ] }, { "name": "text", "data": "）" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n-1" } ] } ] }, { "name": "text", "data": "Pb" }, { "name": "sub", "data": [ { "name": "text", "data": "n" } ] }, { "name": "text", "data": "I" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "3n+1" } ] } ] }, { "name": "text", "data": " （n = 2 and 3） materials， looking down the a-axis" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "52", "type": "bibr", "rid": "R52", "data": [ { "name": "text", "data": "52" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": ". （d） Statistics of grain-size distribution of PPEA" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "FA" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "1-x" } ] } ] }, { "name": "text", "data": "SnI" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": " films with different PPEAI contents" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "53", "type": "bibr", "rid": "R53", "data": [ { "name": "text", "data": "53" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124026&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124028&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124027&type=", "width": "143.33399963", "height": "79.41000366", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "在苯环中引入杂原子，例如F、Cl、Br、O等，可改变配体分子的极性、体积和介电常数等，同时可引入额外的非共价键相互作用。这些变化可对2D钙钛矿的结构和物理化学性质产生显著的影响。Pan等人将F、Cl和Br原子引入PEA中，研究卤素原子对2D钙钛矿的影响" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "54", "type": "bibr", "rid": "R54", "data": [ { "name": "text", "data": "54" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。单晶X射线衍射等表征手段表明卤素原子的引入可降低钙钛矿中无机八面体的扭曲程度以及量子阱和介电限域效应对2D PSCs的影响，从而降低激子结合能。在光伏器件性能上，(pF-PEA)" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "(MA)" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Pb" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "10" } ] }, { "name": "text", "data": "基平面结构PSC实现了5.8%的能量转换效率，优于(H-PEA)" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "(MA)" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Pb" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "10" } ] }, { "name": "text", "data": "基参比器件（" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "a）。2019年，Fu等人采用PEA，pF-PEA和MeO-PEA作为有机配体，并系统地研究了有机配体的尺寸大小对准2D钙钛矿的光电性质和器件性能的影响" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "55", "type": "bibr", "rid": "R55", "data": [ { "name": "text", "data": "55" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。研究表明，大体积（MeO-PEA）或更疏水（pF-PEA）的配体对器件的稳定性起到了积极的作用。另外，pF-PEA和MeO-PEA基2D钙钛矿中的3D成分较多，降低了带隙和激子结合能。由于具有更佳的电荷传输能力和更低的带隙，基于pF-PEAI构建的准2D PSCs（n=5）获得了14.5%的PCE。与此同时，Zhang等人也使用4-氟苯乙胺（pF-PEA）和PEA作为有机配体，并详细地研究了有机配体的堆积结构对2D钙钛矿电荷传输和面外导电能力的影响（" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "b）" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "56", "type": "bibr", "rid": "R56", "data": [ { "name": "text", "data": "56" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。作者发现，氟原子的引入调整了配体分子间的堆积方式，拉近了无机层之间两个苯环分子的距离，进一步改善了无机层的排列，提高了电荷传输和面外导电能力，同时降低了缺陷密度。在不使用任何添加剂和基底预热的条件下，(pF-PEA)" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "(MA)" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "Pb" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "16" } ] }, { "name": "text", "data": "基2D PSCs获得了超过13%的光伏效率，该值远大于(PEA)" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "(MA)" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "Pb" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "16" } ] }, { "name": "text", "data": "的器件效率。此外，Sahayaraj等人使用氨基硫脲添加剂调节pF-PEA基2D钙钛矿晶体的生长和取向，进一步提高了pF-PEA基2D钙钛矿光电性能" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "57", "type": "bibr", "rid": "R57", "data": [ { "name": "text", "data": "57" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。之后，Shao等人使用FA替换MA作A位阳离子，制备了(pF-PEA)" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "(FA)" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "Pb" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "16" } ] }, { "name": "text", "data": "(n=5)基准2D PSCs" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "58", "type": "bibr", "rid": "R58", "data": [ { "name": "text", "data": "58" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。同时，作者使用氯添加剂（MACl和PbCl" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）调节甲脒基钙钛矿的结晶。氯添加剂的引入导致中间相（MAPbCl" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "）的形成。这种中间相可作为晶种辅助α-FAPbI" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "相结晶。通过掠入射广角X射线散射（GIWAXS）和稳态瞬态荧光光谱等表征数据，作者发现α-FAPbI" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "相贯穿整个2D钙钛矿层，并且导致2D相倾斜于基底生长。这种独特的晶体取向和相分布促进了钙钛矿层的电荷迁移和传输（" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "c）。因此，纯FA基2D PSCs实现了创纪录的21%效率（认证效率为20%），Voc损耗仅为0.32 V。该值是RP型2D PSCs领域目前所报道的最高值（" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "d）。" } ] }, { "name": "fig", "data": { "id": "F4", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图4（a）" } ], "title": [ { "name": "text", "data": "H-PEA和pX-PEA（X=F，Cl，Br）基钙钛矿器件的J-V曲线" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "54", "type": "bibr", "rid": "R54", "data": [ { "name": "text", "data": "54" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。（b）pF-PEA" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "MA" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "Pb" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "16" } ] }, { "name": "text", "data": "和PEA" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "MA" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "Pb" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "16" } ] }, { "name": "text", "data": "钙钛矿的晶体结构示意图" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "56", "type": "bibr", "rid": "R56", "data": [ { "name": "text", "data": "56" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。（c）基于MA和FA的二维钙钛矿的晶体取向和相分布的示意图" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "58", "type": "bibr", "rid": "R58", "data": [ { "name": "text", "data": "58" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。（d）高效低维钙钛矿太阳能电池PCE的总结" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "58", "type": "bibr", "rid": "R58", "data": [ { "name": "text", "data": "58" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.4" } ], "title": [ { "name": "text", "data": "（a） J-V curves of H-PEA and pX-PEA （X = F， Cl， Br） perovskite devices" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "54", "type": "bibr", "rid": "R54", "data": [ { "name": "text", "data": "54" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": ". （b） Schematic crystal structures of pF-PEA" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "MA" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "Pb" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "16" } ] }, { "name": "text", "data": " and PEA" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "MA" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "Pb" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "16" } ] }, { "name": "text", "data": " perovskites" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "56", "type": "bibr", "rid": "R56", "data": [ { "name": "text", "data": "56" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": ". （c） The schematic diagrams of the crystal orientation and phase distribution of MA and FA-based 2D perovskites" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "58", "type": "bibr", "rid": "R58", "data": [ { "name": "text", "data": "58" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": ". （d） Summary of the PCE of high-efficiency low-dimensional perovskite solar cells" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "58", "type": "bibr", "rid": "R58", "data": [ { "name": "text", "data": "58" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124029&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124031&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124030&type=", "width": "149.40100098", "height": "84.86100006", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "此外，Yang等人使用3-溴苄基碘化铵（3BBAI）作为有机配体制备2D PSCs。3BBAI的引入调节了相分布，促进了载流子的提取和分离，并获得了18.2％的PCE和长期稳定性" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "59", "type": "bibr", "rid": "R59", "data": [ { "name": "text", "data": "59" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。同时，Liu et al.将氟原子引入苯甲脒的对位，以研究氟原子对2D钙钛矿的物理性能和晶体结构的影响" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "60", "type": "bibr", "rid": "R60", "data": [ { "name": "text", "data": "60" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。与PhFA相比，pF-PhFA基2D PSCs显示出了更长的载流子寿命，更低的非辐射复合损耗，以及改善的电荷载流子迁移率。结果，优化后的器件实现了17.37%的能量转换效率，远高于PhFA基2D PSCs（PCE=12.92%）。更重要的是，由于偶极子-偶极子相互作用以及pF-PhFA与[PbX" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "]" }, { "name": "sup", "data": [ { "name": "text", "data": "4-" } ] }, { "name": "text", "data": "八面体层之间的强氢键作用，pF-PhFA基二维钙钛矿表现出了更优异的稳定性。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "苯环中杂原子的位置和数目也可影响2D钙钛矿的光电性能。Hu等人在苯乙胺（PEA）的不同位置上引入氟原子" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "40", "type": "bibr", "rid": "R40", "data": [ { "name": "text", "data": "40" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，并研究其对2D钙钛矿光伏器件性能的影响。通过对比3-氟苯乙基铵（mF-PEA）、4-氟苯乙基铵（pF-PEA）、2-氟苯乙基铵（oF-PEA）以及苯乙基铵（PEA）基的2D钙钛矿（n=1）的晶体结构，作者发现氟原子的引入改变了分子的偶极矩，从而直接影响了有机阳离子的堆积结构。其中堆积最为有序的pF-PEA基2D钙钛矿器件获得了最高的能量转换效率。由于氟原子的强拉电子效应，五氟苯乙胺（5F-PEA）表现出缺电子的特征，可与富电子的PEA通过π-π相互作用堆积在一起，形成强的电四极矩相互作用。Hu等人使用5F-PEA和PEA的混合物（摩尔比为1:1）作为有机配体，利用这两种分子的电四极矩相互作用合成了具有高稳定性和高性能的准2D钙钛矿（n=4）" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "61", "type": "bibr", "rid": "R61", "data": [ { "name": "text", "data": "61" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。因此，苯环中杂原子的位置和数目可影响芳香族配体之间的相互作用和堆积方式，从而影响薄膜的表面形貌、电荷传输能力和器件性能。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "在DJ型2D钙钛矿领域，苯基有机间隔分子同样得到了广泛的应用。Fang等人研究了具有π共轭结构的芳香族间隔分子对苯二胺（PPDA）和脂肪族间隔分子乙二胺（EDA）对2D钙钛矿性能的影响" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "62", "type": "bibr", "rid": "R62", "data": [ { "name": "text", "data": "62" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。结果表明，相比于乙二胺，(PPDA)Cs" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n-1" } ] } ] }, { "name": "text", "data": "Pb" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "I" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "3n+1" } ] } ] }, { "name": "text", "data": "结构钙钛矿沿着面外的电荷传输能力大幅度增强。如" }, { "name": "xref", "data": { "text": "图5", "type": "fig", "rid": "F5", "data": [ { "name": "text", "data": "图5" } ] } }, { "name": "text", "data": "a所示，这主要是因为：1、碘离子周围的电荷密度较大，导致相邻无机层间的I-I相互作用较强。2、由于PPDA的苯环几乎与I离子的p" }, { "name": "sub", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "和p" }, { "name": "sub", "data": [ { "name": "text", "data": "y" } ] }, { "name": "text", "data": "轨道平行，PPDA与I离子之间存在较强的p-π电子偶联。3、PPDA和I离子之间存在强氢键相互作用。以上三种效应导致新的载流子传输通道的形成，从而加速了面外电荷传输。该研究结果表明芳香族有机分子在准2D钙钛矿的面外电荷传输中起到了关键的作用。Cohen等人使用对苯二甲胺碘盐（BzDAI）作为2D钙钛矿的有机配体制备高效的光伏器件，并获得了15.6%的光伏效率，该值是当时所报道的最高效率之一" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "63", "type": "bibr", "rid": "R63", "data": [ { "name": "text", "data": "63" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。作者认为相比于单胺有机配体，基于双胺有机配体（BzDAI）构建的2D钙钛矿显示出更优的晶体生长方向，其主要原因有以下两点：1、双胺的芳香基团可提供更有序的组装结构。2、双胺有机配体的长度相对较短，这将减少无机框架之间的距离，同时消除或减少了范德华间隙，有利于电荷传输。在FA基2D PSCs领域，BzDAI有机配体同样表现出了优异的性能" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "64", "type": "bibr", "rid": "R64", "data": [ { "name": "text", "data": "64" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。在没有使用添加剂和反溶剂的情况下，(BzDA)FA" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Pb" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "10" } ] }, { "name": "text", "data": "基2D PSCs获得了超过7%的PCE，这是当时纯FA基2D PSCs报道的最高值（" }, { "name": "xref", "data": { "text": "图5", "type": "fig", "rid": "F5", "data": [ { "name": "text", "data": "图5" } ] } }, { "name": "text", "data": "b）。在此基础上，Zheng等人在对苯二甲胺分子中引入4个氟原子，合成了4氟对苯二甲胺（4FBzDA）,并将其用于制备2D钙钛矿太阳能电池 " }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "65", "type": "bibr", "rid": "R65", "data": [ { "name": "text", "data": "65" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。与此同时，Liu等研究发现4F取代的苯双胺配体在2D 钙钛矿中与无机层之间存在多重非共价键相互作用，包括CH···F和F···I等相互作用。多重非共价键的存在提高了2D DJ型钙钛矿的结构稳定性。基于4F取代的苯双胺配体的二维钙钛矿（n=4）太阳能电池获得了16.62%的效率和显著提高的器件稳定性" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "66", "type": "bibr", "rid": "R66", "data": [ { "name": "text", "data": "66" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。Xu等人巧妙地使用混合阳离子PEI" }, { "name": "sup", "data": [ { "name": "text", "data": "+" } ] }, { "name": "text", "data": "和BDA" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "制备了(BDA)" }, { "name": "sub", "data": [ { "name": "text", "data": "0.8" } ] }, { "name": "text", "data": "(PEA" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": ")" }, { "name": "sub", "data": [ { "name": "text", "data": "0.2" } ] }, { "name": "text", "data": "MA" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "Pb" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "X" }, { "name": "sub", "data": [ { "name": "text", "data": "16" } ] }, { "name": "text", "data": "基2D PSCs" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "67", "type": "bibr", "rid": "R67", "data": [ { "name": "text", "data": "67" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。在这种特殊的结构中，BDA分子主要位于钙钛矿晶粒中，因此增强了无机层间的相互作用，消除了范德华间隙，提高了材料的热稳定性；而PEA分子分布在钙钛矿表面，增强了器件湿度稳定性。这种混合阳离子的结构同时结合了DJ型和RP型2D钙钛矿的优势。另外，混合阳离子的引入有利于增强2D钙钛矿的垂直取向、降低缺陷态密度，同时获得均匀分布的量子阱结构，因此器件的效率也得到了明显提升，最高获得了17.21%的光电转化效率。" } ] }, { "name": "fig", "data": { "id": "F5", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图5" } ], "title": [ { "name": "text", "data": "（a）（PPDA）Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "Pb" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "13" } ] }, { "name": "text", "data": "基二维钙钛矿的电荷传输通道示意图" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "62", "type": "bibr", "rid": "R62", "data": [ { "name": "text", "data": "62" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。（b）（BzDA）FA" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Pb" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "10" } ] }, { "name": "text", "data": "基2D PSCs的J-V曲线" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "64", "type": "bibr", "rid": "R64", "data": [ { "name": "text", "data": "64" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。（c）4FBzDA和BzDA的化学结构（左边）。（4FBzDA）PbI" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "的晶体结构（右边）" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "65", "type": "bibr", "rid": "R65", "data": [ { "name": "text", "data": "65" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.5" } ], "title": [ { "name": "text", "data": "（a） The illustration on the three carrier transport channels of （PPDA）Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "Pb" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "13" } ] }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "62", "type": "bibr", "rid": "R62", "data": [ { "name": "text", "data": "62" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": ". （b） J-V curves of the （BzDA）FA" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Pb" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "10" } ] }, { "name": "text", "data": " champion cell" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "64", "type": "bibr", "rid": "R64", "data": [ { "name": "text", "data": "64" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": ". （c） Chemical structures（right） of 4FBzDA and BzDA. and Crystal structure （left） of （4FBzDA）PbI" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "65", "type": "bibr", "rid": "R65", "data": [ { "name": "text", "data": "65" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124032&type=", "small": 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"。同时率先开发了一种甲基氯化铵（MACl）辅助薄膜生长技术，实现了对二维钙钛矿结晶质量和晶体取向的有效调控，获得了近似单晶质量的纳米棒状结构薄膜（图" }, { "name": "xref", "data": { "text": "6", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "6" } ] } }, { "name": "text", "data": "a和" }, { "name": "xref", "data": { "text": "6", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "6" } ] } }, { "name": "text", "data": "b）。这种薄膜具有显著增大的晶粒尺寸和垂直于基底的结晶取向，显著改善了电荷传输特性。采用这种薄膜制备的二维钙钛矿（n=3）光伏器件获得了超过15%的能量转换效率。值得一提的是，该值是当时报道的最高的准2D PSCs效率（n＜6）。与3D器件相比，(ThMA)" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "(MA)" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n-1" } ] } ] }, { "name": "text", "data": "Pb" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "I" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "3n+1" } ] } ] }, { "name": "text", "data": "(n=3)基器件表现出了更优异的长期稳定性。接着，Liu等继续使用ThMA作为有机配体，并将其用于纯FA基2D钙钛矿的制备" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "69", "type": "bibr", "rid": "R69", "data": [ { "name": "text", "data": "69" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。由于阳离子尺寸效应和氢键相互作用，使用甲脒（FA）替换甲胺（MA）作为A位阳离子用于缩小带隙、提高短路电流和能量转换效率被认为是一种有效的策略。在这项工作中，Liu等采用有机盐（4-（三氟甲基）苄基碘化铵，tFM-PMA）辅助结晶的技术（OACG，如" }, { "name": "xref", "data": { "text": "图6", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6" } ] } }, { "name": "text", "data": "c所示）有效地提高了薄膜质量，获得了垂直取向的结晶薄膜，改善了电荷传输，同时抑制了非辐射复合。优化后的(ThMA)" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "(FA)" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "Pb" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "16" } ] }, { "name": "text", "data": "基器件获得19.06%的纪录效率（" }, { "name": "xref", "data": { "text": "图6", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6" } ] } }, { "name": "text", "data": "d）。基于此，Liang等人继续使用ThMA作为有机配体，通过反溶剂沉积法制备了具有反向梯度量子阱结构的FA-MA混合2D钙钛矿薄膜（" }, { "name": "xref", "data": { "text": "图6", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6" } ] } }, { "name": "text", "data": "e）" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "35", "type": "bibr", "rid": "R35", "data": [ { "name": "text", "data": "35" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。这种反向梯度的量子阱结构大大地削弱了量子约束效应。使用该薄膜构建的n-i-p型器件获得了创纪录的PCE（20.12%）。该值是2D PSCs（n＜20）领域所报道的最高PCE值之一。同时，器件的稳定性也得到了显著的提高，未封装的设备在30%相对湿度（RH）下老化2000小时后，仍保持98%的效率，在最大功率点连续运行360小时后保持96%的效率。Ni等人对比了噻吩基和传统的苯基二维钙钛矿，发现噻吩甲胺配体的引入改善了无机层与有机配体之间的电荷转移，使得噻吩基二维钙钛矿表现出了更优异的光电性能" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "70", "type": "bibr", "rid": "R70", "data": [ { "name": "text", "data": "70" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "fig", "data": { "id": "F6", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图6" } ], "title": [ { "name": "text", "data": "（a）（ThMA）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "（MA）" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n-1" } ] } ] }, { "name": "text", "data": "Pb" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "I" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "3n+1" } ] } ] }, { "name": "text", "data": "（n=3）钙钛矿堆积结构示意图" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "68", "type": "bibr", "rid": "R68", "data": [ { "name": "text", "data": "68" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。（b）ThMA基2D钙钛矿器件的界面SEM图" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "68", "type": "bibr", "rid": "R68", "data": [ { "name": "text", "data": "68" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。（c）使用tFM-PMA辅助结晶（OACG）和其他方法制备噻吩基准2D PSCs示意图" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "69", "type": "bibr", "rid": "R69", "data": [ { "name": "text", "data": "69" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。（d）基于OACG和参比方法制备的2D PSCs的J-V曲线。（e）ThMA基2D钙钛矿薄膜形成过程示意图" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "35", "type": "bibr", "rid": "R35", "data": [ { "name": "text", "data": "35" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.6" } ], "title": [ { "name": "text", "data": "（a） Proposed packing structures of （ThMA）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "（MA）" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n-1" } ] } ] }, { "name": "text", "data": "Pb" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "I" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "3n+1" } ] } ] }, { "name": "text", "data": " （n=3） " }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "68", "type": "bibr", "rid": "R68", "data": [ { "name": "text", "data": "68" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": ". （b） Cross-section SEM image of the ThMA-based 2D perovskite device" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "68", "type": "bibr", "rid": "R68", "data": [ { "name": "text", "data": "68" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": ". （c） Procedures of preparation quasi-2D RP perovskite films using OACG and other processing methods" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "69", "type": "bibr", "rid": "R69", "data": [ { "name": "text", "data": "69" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": ". （d） J-V curves of quasi-2D RP PSCs based on the control and OACG-processed films. （e） Schematic diagrams of the film formation process of ThMA-based 2D perovskite" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "35", "type": "bibr", "rid": "R35", "data": [ { "name": "text", "data": "35" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124035&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124037&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124036&type=", "width": "149.86000061", "height": "81.77400208", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "由于FA可显著减小带隙，提高效率和稳定性，因此Liu等报道了一种FA基有机配体（噻吩甲脒，ThFA），并将其用于制备2D RP型PSCs" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "71", "type": "bibr", "rid": "R71", "data": [ { "name": "text", "data": "71" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。此外，Liu等同时开发了一种前驱体有机盐辅助晶体生长（PACG）的方法。如" }, { "name": "xref", "data": { "text": "图7", "type": "fig", "rid": "F7", "data": [ { "name": "text", "data": "图7" } ] } }, { "name": "text", "data": "a所示，将含有ThFAI、MAI、和MACl的稀IPA溶液作为反溶剂旋涂于薄膜表面。该方法可诱导晶体生长和取向，并调节薄膜质量和相分布，从而延长载流子寿命，改善载流子迁移率，抑制非辐射复合损耗。基于此，(ThFA)" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "(MA)" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n-1" } ] } ] }, { "name": "text", "data": "Pb" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "I" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "3n+1" } ] } ] }, { "name": "text", "data": "(n=3)基器件获得了最高16.72%的PCE，且稳定性也得到了显著的提高。接着，Liu等将ThMA和ThFA有机配体引入二维全无机钙钛矿中，同样获得了优异的光伏性能，和提高的器件稳定性（" }, { "name": "xref", "data": { "text": "图7", "type": "fig", "rid": "F7", "data": [ { "name": "text", "data": "图7" } ] } }, { "name": "text", "data": "b）" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "72", "type": "bibr", "rid": "R72", "data": [ { "name": "text", "data": "72" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。研究发现，噻吩基配体的引入可以释放了无机钙钛矿结构中的内应力，从而显著地提高了材料的相稳定性，实现其从亚稳态γ相三维CsPbI" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "到稳态二维钙钛矿的转变。更重要的是，ThFA基2D RP型全无机钙钛矿(ThFA)" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "(Cs)" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n-1" } ] } ] }, { "name": "text", "data": "Pb" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "I" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "3n+1" } ] } ] }, { "name": "text", "data": "(ThFA-Cs, n=5)具有更均匀的相分布，更低的陷阱密度、更小的激子结合能以及垂直方向的晶体取向，这促进了电荷的提取和分离。最终器件获得了16.00%的出色效率。" } ] }, { "name": "fig", "data": { "id": "F7", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图7" } ], "title": [ { "name": "text", "data": "（a）（ThFA）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "MA" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Pb" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "10" } ] }, { "name": "text", "data": "钙钛矿结构和ThFA基2D钙钛矿薄膜制备过程示意图" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "71", "type": "bibr", "rid": "R71", "data": [ { "name": "text", "data": "71" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。（b）噻吩基有机配体用于释放CsPbI" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "钙钛矿应力示意图" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "72", "type": "bibr", "rid": "R72", "data": [ { "name": "text", "data": "72" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。（c）沿方位角绘制的Q" }, { "name": "sub", "data": [ { "name": "text", "data": "xy" } ] }, { "name": "text", "data": "为1.0 Å" }, { "name": "sup", "data": [ { "name": "text", "data": "–1" } ] }, { "name": "text", "data": "（111）平面的衍射强度分布图" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "73", "type": "bibr", "rid": "R73", "data": [ { "name": "text", "data": "73" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。（d）单晶胶体相在不同溶剂中转变成随机或高晶体取向的RPP薄膜" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "75", "type": "bibr", "rid": "R75", "data": [ { "name": "text", "data": "75" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.7" } ], "title": [ { "name": "text", "data": "（a） 3D chemical structure of ThFA and schematic structure of （ThFA）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "MA" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Pb" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "10" } ] }, { "name": "text", "data": ". And schematic diagram of the fabrication process for ThFA-based 2D perovskite films" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "71", "type": "bibr", "rid": "R71", "data": [ { "name": "text", "data": "71" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": ". （b） Stress release by introducing the thiophene-based spacer" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "72", "type": "bibr", "rid": "R72", "data": [ { "name": "text", "data": "72" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": ". （c） Intensity of （111） plane corresponding to a Q" }, { "name": "sub", "data": [ { "name": "text", "data": "xy" } ] }, { "name": "text", "data": " of 1.0 Å" }, { "name": "sup", "data": [ { "name": "text", "data": "–1" } ] }, { "name": "text", "data": " plotted along azimuthal angle" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "73", "type": "bibr", "rid": "R73", "data": [ { "name": "text", "data": "73" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": ". （d） Diagram showing the transformation of colloidal phase into either random or highly oriented RPP films from single-crystal starting material in various solvents" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "75", "type": "bibr", "rid": "R75", "data": [ { "name": "text", "data": "75" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124038&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124040&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124039&type=", "width": "147.69000244", "height": "72.00199890", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "由于量子约束和介电限域效应，2D钙钛矿通常具有较宽的带隙和较差的电荷传输能力。为了解决这个问题，需要调节准二维钙钛矿中相的分布以及晶体的取向。另外，延长共轭环的长度，提高有机配体的介电常数也是一种可行方案。Dou等人使用大体积的联噻吩乙胺盐（2T）作为有机配体，同时开发了一种三组分的有机溶剂体系（GBL-DMSO-MeOH），成功地改善了二维钙钛矿晶体的垂直取向（" }, { "name": "xref", "data": { "text": "图7", "type": "fig", "rid": "F7", "data": [ { "name": "text", "data": "图7" } ] } }, { "name": "text", "data": "c）和相纯度。由于大体积的2T分子的存在，器件的湿度稳定性也得到了明显的提高" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "73", "type": "bibr", "rid": "R73", "data": [ { "name": "text", "data": "73" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。此外，Yan等人发现含S原子的噻吩乙胺（ThEA）可用于调节2D钙钛矿中的相结构，促进3D相自发地产生" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "74", "type": "bibr", "rid": "R74", "data": [ { "name": "text", "data": "74" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。Pb和S之间的强相互作用压缩了钙钛矿晶格，诱导了2D钙钛矿晶界处3D相的成核和生长。由于3D相的存在降低了带隙，提供了额外的电荷传输路径。ThEA基准二维钙钛矿具有更长的激子扩散长度和载流子寿命，并且显示出了7.20%的PCE和显著提高的稳定性。为了进一步调节ThEA基钙钛矿的结晶度和晶体取向，采用了NH" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "Cl添加剂和二甲基亚砜溶剂（DMSO）双重处理的方法，获得了11.32%的PCE。另外，如" }, { "name": "xref", "data": { "text": "图7", "type": "fig", "rid": "F7", "data": [ { "name": "text", "data": "图7" } ] } }, { "name": "text", "data": "（d）所示，Qin等人使用合成的(ThEA)" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "(MA)" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Pb" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "10" } ] }, { "name": "text", "data": "单晶，并将其溶解在二甲基乙酰胺（DMAc）：甲苯（TOL）：碘化氢（HI）的混合溶剂中制备钙钛矿薄膜的前体溶液" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "75", "type": "bibr", "rid": "R75", "data": [ { "name": "text", "data": "75" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。HI的加入降低了PbI" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "和DMAc之间的相互作用，缓解了2D层状单晶的分解。同时，层状单晶结构可通过不良溶剂甲苯保持聚集的状态，以稳定溶液中n=3的2D结构。使用这种方法获得了具有较窄的相分布和垂直晶体取向的2D钙钛矿薄膜，同时器件的性能和重复性也得到了改善。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "上文介绍了噻吩类有机配体在RP结构2D PSCs中独特的作用，其已被证实适用于RP型2D PSCs光伏器件的制备。另一方面，噻吩衍生物同样适用于DJ型2D钙钛矿的制备。如" }, { "name": "xref", "data": { "text": "图8", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8" } ] } }, { "name": "text", "data": "a所示，Liu等首次使用噻吩衍生物，2，5-噻吩二甲基铵（ThDMA），作为有机配体用于制备DJ型2D PSCs" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "77", "type": "bibr", "rid": "R77", "data": [ { "name": "text", "data": "77" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。作者系统地研究了前驱体溶液（DMF和DMSO）对薄膜质量的影响，并提出了电荷传输模型（" }, { "name": "xref", "data": { "text": "图8", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8" } ] } }, { "name": "text", "data": "b），最终ThDMA基的2D DJ型钙钛矿获得了15.75%的能量转化效率。重要的是，由于消除了有机分子间的范德华间隙，器件光照稳定性和热稳定性均得到了显著提高。基于以上研究成果，Liu等进一步合成了一种稠环噻吩基间配体，噻吩并[3，2-b]噻吩-2，5-二甲基胺碘化物（TTDMAI），并将其用于制备DJ型2D PSCs，最终获得了高达18.82%的PCE" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "76", "type": "bibr", "rid": "R76", "data": [ { "name": "text", "data": "76" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。与ThDMA相比，TTDMA配体的长π共轭结构提高了介电常数，减小了与无机层之间的介电失配和激子结合能，这有利于电荷的分离的提取。另外，由于强分子间相互作用导致的模板效应，基于TTDMA制备的薄膜表现出了垂直方向的晶体生长（" }, { "name": "xref", "data": { "text": "图8", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8" } ] } }, { "name": "text", "data": "c）。这些研究工作展示了噻吩基配体在2D钙钛矿领域的巨大潜力。然而，噻吩基配体及其对二维钙钛矿性能影响的研究相对较少，需要进一步的开发和研究。" } ] }, { "name": "fig", "data": { "id": "F8", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图8" } ], "title": [ { "name": "text", "data": "（a）MA，ThDMA和TDMA的化学结构；（ThDMA）（MA）" }, { "name": "sub", "data": [ { "name": "text", "data": "n-1" } ] }, { "name": "text", "data": "Pb" }, { "name": "sub", "data": [ { "name": "text", "data": "n" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "3n+1" } ] }, { "name": "text", "data": "（n=4）的晶体结构示意图" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "76", "type": "bibr", "rid": "R76", "data": [ { "name": "text", "data": "76" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。（b）ThDMA基2D钙钛矿形貌和电荷传递模型示意图" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "77", "type": "bibr", "rid": "R77", "data": [ { "name": "text", "data": "77" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。（c）ThDMA-Pb和TTDMA-Pb薄膜的能量传递动力学示意图" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "76", "type": "bibr", "rid": "R76", "data": [ { "name": "text", "data": "76" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.8" } ], "title": [ { "name": "text", "data": "（a） 3D chemical structures of MA， ThDMA and TTDMA， and schematic crystal structures of （ThDMA）（MA）" }, { "name": "sub", "data": [ { "name": "text", "data": "n-1" } ] }, { "name": "text", "data": "Pb" }, { "name": "sub", "data": [ { "name": "text", "data": "n" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "3n+1" } ] }, { "name": "text", "data": " （nominal n = 4， ThDMAPb）" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "76", "type": "bibr", "rid": "R76", "data": [ { "name": "text", "data": "76" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": ". （b） Schematic diagram of morphology and charge transport model of the ThDMA-based 2D perovskite devices" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "77", "type": "bibr", "rid": "R77", "data": [ { "name": "text", "data": "77" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": ". （c） Schematic diagrams of energy transfer dynamics of ThDMA-Pb and TTDMA-Pb films" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "76", "type": "bibr", "rid": "R76", "data": [ { "name": "text", "data": "76" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124041&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124043&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124042&type=", "width": "149.30828857", "height": "72.66479492", "fontsize": "" } ] } } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.3　其他芳香族配体在2D PSCs领域的应用" } ], "level": "2", "id": "s3c" } }, { "name": "p", "data": [ { "name": "text", "data": "在2D钙钛矿领域，除了苯环和噻吩，最受关注的芳香基团还包括吡啶、咪唑、呋喃、萘和芘等，这些分子均具有其独特的性质。例如，吡啶环上的N原子可与钙钛矿中Pb" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子发生较强的络合作用（" }, { "name": "xref", "data": { "text": "图9", "type": "fig", "rid": "F9", "data": [ { "name": "text", "data": "图9" } ] } }, { "name": "text", "data": "a），从而延缓结晶速率，提高薄膜质量和器件性能" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "78", "type": "bibr", "rid": "R78", "data": [ { "name": "text", "data": "78" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。Zheng等将呋喃甲胺氢碘酸盐（FuMAI）用于制备2D PSCs，并获得了15.24%的能量转换效率" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "79", "type": "bibr", "rid": "R79", "data": [ { "name": "text", "data": "79" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。Liu等报道了呋喃甲胺氢碘酸盐(FuMACl)并应用于二维钙钛矿。研究发现n=4的二维钙钛矿具有18.0 µs的超长载流子寿命，PCE达到18.00%。这主要归因于FuMA基2D PSCs材料中较低的激子结合能和电子-声子耦合系数" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "80", "type": "bibr", "rid": "R80", "data": [ { "name": "text", "data": "80" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。此外，Febriansyah等人采用吡啶鎓乙胺碘盐（PyrEA）和咪唑乙胺碘盐（ImEA）作为2D钙钛矿的有机配体（" }, { "name": "xref", "data": { "text": "图9", "type": "fig", "rid": "F9", "data": [ { "name": "text", "data": "图9" } ] } }, { "name": "text", "data": "b），打破了n=1器件的记录效率（1.38%），并获得了当时最高的PCE（1.83%）" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "81", "type": "bibr", "rid": "R81", "data": [ { "name": "text", "data": "81" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。在这项研究中，作者发现与苯乙胺相比，PyrEA和ImEA具有更低的电荷密度，导致[PbI" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "]" }, { "name": "sup", "data": [ { "name": "text", "data": "4-" } ] }, { "name": "text", "data": "八面体的扭曲角度变小（" }, { "name": "xref", "data": { "text": "图9", "type": "fig", "rid": "F9", "data": [ { "name": "text", "data": "图9" } ] } }, { "name": "text", "data": "c），从而降低了2D钙钛矿的带隙，提高了器件的短路电流。另一方面，不同于单胺分子，PyrEA和ImEA拉近了无机层之间的间距，增强了2D钙钛矿的面外电导率。" } ] }, { "name": "fig", "data": { "id": "F9", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图9" } ], "title": [ { "name": "text", "data": "（a）4-AEPI、PbI" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "/4-AEPI和PbI" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "/2（4-AEPI）的XPS光谱" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "78", "type": "bibr", "rid": "R78", "data": [ { "name": "text", "data": "78" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。（b）PyrEA，ImEA和PEA的分子结构" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "81", "type": "bibr", "rid": "R81", "data": [ { "name": "text", "data": "81" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。（c）（PyrEA）PbI" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "、（ImEA）PbI" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "和（PEA）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "PbI" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "的单晶X射线结构" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "81", "type": "bibr", "rid": "R81", "data": [ { "name": "text", "data": "81" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.9" } ], "title": [ { "name": "text", "data": "（a） XPS spectra of Pb 4f and N 1s for 4-AEPI， PbI" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "， PbI" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "/4-AEPI， and PbI" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "/2（4-AEPI）" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "78", "type": "bibr", "rid": "R78", "data": [ { "name": "text", "data": "78" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": ". （b） Molecular structures of the dications PyrEA， ImEA， and PEA" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "81", "type": "bibr", "rid": "R81", "data": [ { "name": "text", "data": "81" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": ". （c） Single crystal X-ray structures of 2D perovskites （PyrEA）PbI" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "， （ImEA）PbI" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "， and （PEA）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "PbI" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "81", "type": "bibr", "rid": "R81", "data": [ { "name": "text", "data": "81" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124044&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124046&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124045&type=", "width": "146.67486572", "height": "74.12916565", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "受3-（氨甲基）哌啶（3AMP）和4-（氨甲基）哌啶（4AMP）的启发" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "44", "type": "bibr", "rid": "R44", "data": [ { "name": "text", "data": "44" } ] } }, { "name": "text", "data": ", " }, { "name": "xref", "data": { "text": "82", "type": "bibr", "rid": "R82", "data": [ { "name": "text", "data": "82" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，Li等人使用两种新型芳香族配体3-（氨甲基）吡啶（3AMPY）和4-（氨甲基）吡啶（4AMPY）以探索间隔分子的对称性、构象以及共轭结构对2D钙钛矿晶体结构和光学性质的影响" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "83", "type": "bibr", "rid": "R83", "data": [ { "name": "text", "data": "83" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。作者认为，AMPY分子具有与AMP相同的体积和类似的分子结构，但是前者具有共轭结构，而后者为非共轭结构，这将为AMPY类分子引入一些新的特征，例如高的介电常数，增强的阳离子刚性以及离域的正电荷等。这些特征可以调节无机层内静电相互作用以及与周围环境的氢键作用，从而调节无机层的结构和电子特性（" }, { "name": "xref", "data": { "text": "图10", "type": "fig", "rid": "F10", "data": [ { "name": "text", "data": "图10" } ] } }, { "name": "text", "data": "a）。在这项研究中，作者首先发现4AMPY基2D钙钛矿具有与3AMPY不同的结构细节。3AMPY分子的对称性较差，导致晶体结构中无机层略有偏移，而对称性较好的4AMPY基晶体中没有这种偏移。偏移的产生使得3AMPY基2D钙钛矿[PbI" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "]" }, { "name": "sup", "data": [ { "name": "text", "data": "4-" } ] }, { "name": "text", "data": "八面体倾斜减少，从而降低了带隙。其次，作者对比了共轭结构对钙钛矿晶体和光学性质的影响。相比脂肪族AMP体系，具有共轭结构的AMPY母核中的C-C键较短，这拉近了晶体中无机层之间的距离（＜4Å）。另一方面，由于共轭结构的存在，AMPY分子具有更高的介电常数和更低的激子结合能。得益于以上优势，基于(3AMPY)(MA)" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "Pb" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "13" } ] }, { "name": "text", "data": "的器件获得了9.2%的效率。这项研究表明有机配体的共轭结构、对称性以及构象等均可对2D钙钛矿的晶体结构和性能产生影响。" } ] }, { "name": "fig", "data": { "id": "F10", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图10" } ], "title": [ { "name": "text", "data": "（a）（3AMPY）（MA）Pb" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "7" } ] }, { "name": "text", "data": "和（4AMPY）（MA）Pb" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "7" } ] }, { "name": "text", "data": "单晶结构对比" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "83", "type": "bibr", "rid": "R83", "data": [ { "name": "text", "data": "83" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。（b）9种包含萘、芘、苝和脂肪链的钙钛矿（n=1）的面外电导率" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "38", "type": "bibr", "rid": "R38", "data": [ { "name": "text", "data": "38" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.10" } ], "title": [ { "name": "text", "data": "（a） Structural comparison of （3AMPY）（MA）Pb" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "7" } ] }, { "name": "text", "data": " and （4AMPY）（MA）Pb" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "7" } ] }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "83", "type": "bibr", "rid": "R83", "data": [ { "name": "text", "data": "83" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": ". （b） Out-of-plane conductivity of nine different n = 1 layered perovskites with either an aliphatic cation or a cation containing naphthalene， pyrene， or perylene" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "38", "type": "bibr", "rid": "R38", "data": [ { "name": "text", "data": "38" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124047&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124049&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=37124048&type=", "width": "158.94201660", "height": "81.76995087", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "萘、蒽和芘等也被用于构建2D钙钛矿太阳能电池" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "38", "type": "bibr", "rid": "R38", "data": [ { "name": "text", "data": "38" } ] } }, { "name": "text", "data": ", " }, { "name": "xref", "data": { "text": "84", "type": "bibr", "rid": "R84", "data": [ { "name": "text", "data": "84" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。如" }, { "name": "xref", "data": { "text": "图10", "type": "fig", "rid": "F10", "data": [ { "name": "text", "data": "图10" } ] } }, { "name": "text", "data": "b所示，2018年Passarelli等人合成了6种具有“Aromatic-O-Linker-NH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "”结构的多环芳香族阳离子，并研究了其电子性质和结构排列对2D钙钛矿性能的影响" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "38", "type": "bibr", "rid": "R38", "data": [ { "name": "text", "data": "38" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。对比这几种芳香基和脂肪基2D钙钛矿（n=1）后，作者发现随着层间距的增加，面外电导率逐渐降低。另外，分子的堆积结构对2D钙钛矿面外电导率也起着较为关键的影响。芘分子形成的“边对面”的构型要比“边对边”结构更有利于面外电导率的提高。然而，采用“边对边”堆积结构的(perylene-O-ethyl-NH)" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "PbI" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "却表现出最高的面外电导率，这主要是因为perylene-O-ethyl-NH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "与无机层具有更优的能级排列。通过优化面外电导率，作者获得了当时2D PSCs（n=1）最高1.38%的能量转换效率。以上结果表明，芳香族有机配体具有比脂肪族更优的导电能力，并且可以通过改变芳香基团的电子性质和堆积结构获得最优的器件性能。Liu等使用多环芳香结构，1-萘甲基铵（NpMA）和9-蒽甲基铵（AnMA）作为配体，制备了2D PSC（n=4），并分别实现了17.25%和14.47%的PCE" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "84", "type": "bibr", "rid": "R84", "data": [ { "name": "text", "data": "84" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。其中，基于NpMA的2D PSC获得了1.24 V的高开路电压。通过瞬态吸收光谱研究，作者发现基于萘基配体的2D钙钛矿中存在二维相到三维相的超快电荷/能量转移过程（~7 ps）。这一发现为具有较大激子结合能的二维钙钛矿仍然可以实现较高的光伏效率提供了理论支撑。尽管多环芳香族配体已经被应用于2D PSCs领域，并表现出一些独特的性质，但因溶解度问题，多环芳香族配体的使用仍然较少，需要进一步系统的研究。" } ] } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "4　总结与展望" } ], "level": "1", "id": "s4" } }, { "name": "p", "data": [ { "name": "text", "data": "与3D钙钛矿相比，2D钙钛矿材料具有优异的结构和环境稳定性。然而，目前2D PSCs的能量转换效率仍低于传统的3D PSCs。其中影响二维钙钛矿光伏效率的关键因素包括：1、多种相同时存在且随机分布，不利于电荷传输。2、量子阱和介电效应导致较大的激子结合能抑制了电荷的有效分离。因此，合理地设计和选择有机配体是提高2D PSCs效率的关键。本文通过系统地归纳芳香族配体自身的优势以及芳香族配体的结构对钙钛矿晶体取向、介电限域效应、激子结合能、量子阱的分布以及光电性能等方面的影响，总结了面向高效二维钙钛矿PSCs的有机配体的几点设计原则：" } ] }, { "name": "p", "data": [ { "name": "text", "data": "1、选择芳香族化合物。相比于脂肪族分子，具有高介电常数的长共轭配体可减小与无机层之间的介电失配，并降低激子结合能同时改善电荷传输。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2、设计双胺芳香族配体。由于具有更小的范德华间隙和更短的无机层之间的距离，DJ型二维钙钛矿表现出了独特的光电性能和稳定性。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "3、引入合适的分子间相互作用。有机配体之间以及有机配体与无机[PbI" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "]" }, { "name": "sup", "data": [ { "name": "text", "data": "4-" } ] }, { "name": "text", "data": "之间的相互作用影响着钙钛矿晶体结构和光电性能，而杂原子的引入能增强分子间的相互作用、提高钙钛矿的稳定性。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "此外，在选定有机配体之后，需要进一步优化薄膜制备工艺，如：溶剂的种类、反溶剂处理方法和化学添加剂等条件以调控晶体取向和量子阱分布。虽然2D钙钛矿器件的效率仍低于3D器件，但近几年来，2D PSCs的效率在不断地提升，目前已经达到22%的水平，表现出了巨大的潜力。我们认为在不久的将来2D PSCs的PCE可以与3D PSCs相媲美，进一步推动稳定高效PSCs的发展和产业化应用。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "本文（补充文件及）专家审稿意见和作者回复内容下载地址：" }, { "name": "extlink", "data": { "text": [ { "name": "text", "data": 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