Wang Wenran, Zhang Meng, Pan Zhenxiao, Biesold Gill M, Liang Shuang, Rao Huashang, Lin Zhiqun, Zhong Xinhua
Key Laboratory for Biobased Materials and Energy of Ministry of Education, College of Materials and Energy, South China Agricultural University, 483 Wushan Road, Guangzhou 510642, China.
School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332, United States.
Chem Rev. 2022 Feb 9;122(3):4091-4162. doi: 10.1021/acs.chemrev.1c00478. Epub 2021 Dec 30.
Colloidal nanocrystals (NCs) are intriguing building blocks for assembling various functional thin films and devices. The electronic, optoelectronic, and thermoelectric applications of solution-processed, inorganic ligand (IL)-capped colloidal NCs are especially promising as the performance of related devices can substantially outperform their organic ligand-capped counterparts. This in turn highlights the significance of preparing IL-capped NC dispersions. The replacement of initial bulky and insulating ligands capped on NCs with short and conductive inorganic ones is a critical step in solution-phase ligand exchange for preparing IL-capped NCs. Solution-phase ligand exchange is extremely appealing due to the highly concentrated NC inks with completed ligand exchange and homogeneous ligand coverage on the NC surface. In this review, the state-of-the-art of IL-capped NCs derived from solution-phase inorganic ligand exchange (SPILE) reactions are comprehensively reviewed. First, a general overview of the development and recent advancements of the synthesis of IL-capped colloidal NCs, mechanisms of SPILE, elementary reaction principles, surface chemistry, and advanced characterizations is provided. Second, a series of important factors in the SPILE process are offered, followed by an illustration of how properties of NC dispersions evolve after ILE. Third, surface modifications of perovskite NCs with use of inorganic reagents are overviewed. They are necessary because perovskite NCs cannot withstand polar solvents or undergo SPILE due to their soft ionic nature. Fourth, an overview of the research progresses in utilizing IL-capped NCs for a wide range of applications is presented, including NC synthesis, NC solid and film fabrication techniques, field effect transistors, photodetectors, photovoltaic devices, thermoelectric, and photoelectrocatalytic materials. Finally, the review concludes by outlining the remaining challenges in this field and proposing promising directions to further promote the development of IL-capped NCs in practical application in the future.
胶体纳米晶体(NCs)是用于组装各种功能薄膜和器件的有趣构建块。溶液处理的、无机配体(IL)封端的胶体NCs在电子、光电和热电应用方面尤其具有前景,因为相关器件的性能能够显著优于其有机配体封端的对应物。这反过来凸显了制备IL封端的NC分散体的重要性。用短而导电的无机配体取代最初包覆在NCs上的庞大且绝缘的配体,是制备IL封端的NCs的溶液相配体交换中的关键步骤。溶液相配体交换极具吸引力,因为其能实现配体交换完全且NC表面配体覆盖均匀的高浓度NC墨水。在本综述中,全面回顾了源自溶液相无机配体交换(SPILE)反应的IL封端的NCs的研究现状。首先,对IL封端的胶体NCs的合成发展及近期进展、SPILE的机制、基本反应原理、表面化学和先进表征进行了总体概述。其次,介绍了SPILE过程中的一系列重要因素,随后说明了ILE后NC分散体的性质如何演变。第三,概述了使用无机试剂对钙钛矿NCs进行的表面改性。这是必要的,因为钙钛矿NCs由于其软离子性质,无法耐受极性溶剂或进行SPILE。第四,介绍了利用IL封端的NCs在广泛应用中的研究进展,包括NC合成、NC固体和薄膜制造技术、场效应晶体管、光电探测器、光伏器件、热电和光电催化材料。最后,本综述通过概述该领域尚存的挑战并提出有前景的方向来作结,以在未来进一步推动IL封端的NCs在实际应用中的发展。