3D Printing of Ruddlesden-Popper Perovskites with High Color Purity and Stability

Ruddlesden–Popper (RP) lead halide perovskites have emerged as a new class of tunable two-dimensional semiconductors that demonstrate high performance in optoelectronics due to their enhanced stability and structural tunability^1,2. The nanostructured RP perovskites with forms of films or wires are the basic building blocks for manufacturing high-density integration of optoelectronic circuitries and devices^3,4. However, their nanostructures are limited due to the complex organic−inorganic layered crystalline features⁵. Some clever methods based on template growth⁶, lithography⁷, inkjet printing⁸ and chemical vapor deposition⁹ have been devised to produce RP perovskite nanostructures but new methods are still in great demand for high-resolution, three-dimensional integration. Furthermore, the engineering challenges associated with how to engineer the perovskite phase in the nanostructure still remains unresolved¹⁰. Here, we report a nanoscale 3D printing method for RP perovskites with programmed shape and crystallinity. The method exploits a femtoliter precursor meniscus formed on a nanopipette to guide RP perovskite crystallization at will under strong evaporation of solvent. Guiding the meniscus in three-dimension leads to the formation of a freeform, freestanding RP perovskite nanowire exhibiting a polycrystalline nature. It is observed that the crystalline feature is successfully controlled in in-situ by adjusting temperature and humidity during the 3D printing process. In this talk, I will present my research progress on the development of 3D printing for RP perovskites and discuss prospects of our work for potential applications in electronics and optoelectronics.<br/><b>References</b><br/>1 Pan, D.<i> et al.</i> Deterministic fabrication of arbitrary vertical heterostructures of two dimensional Ruddlesden-Popper halide perovskites. <i>Nat Nanotechnol</i> <b>16</b>, 159-165, doi:10.1038/s41565-020-00802-2 (2021).<br/>2 Blancon, J. C., Even, J., Stoumpos, C. C., Kanatzidis, M. G. & Mohite, A. D. Semiconductor physics of organic-inorganic 2D halide perovskites. <i>Nat Nanotechnol</i> <b>15</b>, 969-985, doi:10.1038/s41565-020-00811-1 (2020).<br/>3 Quan, L. N., Kang, J., Ning, C.-Z. & Yang, P. Nanowires for Photonics. <i>Chemical Reviews</i> <b>119</b>, 9153-9169, doi:10.1021/acs.chemrev.9b00240 (2019).<br/>4 Chen, J.<i> et al.</i> Oriented Halide Perovskite Nanostructures and Thin Films for Optoelectronics. <i>Chem Rev</i>, doi:10.1021/acs.chemrev.1c00181 (2021).<br/>5 Li, X., Hoffman, J. M. & Kanatzidis, M. G. The 2D Halide Perovskite Rulebook: How the Spacer Influences Everything from the Structure to Optoelectronic Device Efficiency. <i>Chem Rev</i> <b>121</b>, 2230-2291, doi:10.1021/acs.chemrev.0c01006 (2021).<br/>6 Feng, J.<i> et al.</i> Single-crystalline layered metal-halide perovskite nanowires for ultrasensitive photodetectors. <i>Nature Electronics</i> <b>1</b>, 404-410, doi:10.1038/s41928-018-0101-5 (2018).<br/>7 Qin, C.<i> et al.</i> Stable room-temperature continuous-wave lasing in quasi-2D perovskite films. <i>Nature</i> <b>585</b>, 53-57, doi:10.1038/s41586-020-2621-1 (2020).<br/>8 Jia, S.<i> et al.</i> Highly Luminescent and Stable Green Quasi 2D Perovskite Embedded Polymer Sheets by Inkjet Printing. <i>Advanced Functional Materials</i> <b>30</b>, doi:10.1002/adfm.201910817 (2020).<br/>9 Ghoshal, D.<i> et al.</i> Catalyst Free and Morphology Controlled Growth of 2D Perovskite Nanowires for Polarized Light Detection. <i>Advanced Optical Materials</i> <b>7</b>, doi:10.1002/adom.201900039 (2019).<br/>10 Liang, C.<i> et al.</i> Two-dimensional Ruddlesden-Popper layered perovskite solar cells based on phase-pure thin films. <i>Nature Energy</i> <b>6</b>, 38-+, doi:10.1038/s41560-020-00721-5 (2021).