Theory-Guided Synthesis of Highly Luminescent Colloidal Cesium Tin Halide Perovskite Nanocrystals
- 1 April 2021
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 143 (14), 5470-5480
- https://doi.org/10.1021/jacs.1c01049
Abstract
The synthesis of highly luminescent colloidal CsSnX3 (X = halogen) perovskite nanocrystals (NCs) remains a long-standing challenge due to the lack of a fundamental understanding of how to rationally suppress the formation of structural defects that significantly influence the radiative carrier recombination processes. Here, we develop a theory-guided, general synthetic concept for highly luminescent CsSnX3 NCs. Guided by density functional theory calculations and molecular dynamics simulations, we predict that, although there is an opposing trend in the chemical potential-dependent formation energies of various defects, highly luminescent CsSnI3 NCs with narrow emission could be obtained through decreasing the density of tin vacancies. We then develop a colloidal synthesis strategy that allows for rational fine-tuning of the reactant ratio in a wide range but still leads to the formation of CsSnI3 NCs. By judiciously adopting a tin-rich reaction condition, we obtain narrow-band-emissive CsSnI3 NCs with a record emission quantum yield of 18.4%, which is over 50 times larger than those previously reported. Systematic surface-state characterizations reveal that these NCs possess a Cs/I-lean surface and are capped with a low density of organic ligands, making them an excellent candidate for optoelectronic devices without any postsynthesis ligand management. We showcase the generalizability of our concept by further demonstrating the synthesis of highly luminescent CsSnI2.5Br0.5 and CsSnI2.25Br0.75 NCs. Our findings not only highlight the value of computation in guiding the synthesis of high-quality colloidal perovskite NCs but also could stimulate intense efforts on tin-based perovskite NCs and accelerate their potential applications in a range of high-performance optoelectronic devices.Keywords
Funding Information
- Japan Society for the Promotion of Science (19K22176)
- Japan Science and Technology Agency (JPMJTS1619)
- National Natural Science Foundation of China (11874275)
This publication has 62 references indexed in Scilit:
- Nanocrystals of Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color GamutNano Letters, 2015
- Trioctylphosphine as self-assembly inducerFaraday Discussions, 2014
- Influence of Defects and Synthesis Conditions on the Photovoltaic Performance of Perovskite Semiconductor CsSnI3Chemistry of Materials, 2014
- Electronic band structure, phonons, and exciton binding energies of halide perovskites CsSnCl, CsSnBr, and CsSnIPhysical Review B, 2013
- CsSnI3: Semiconductor or Metal? High Electrical Conductivity and Strong Near-Infrared Photoluminescence from a Single Material. High Hole Mobility and Phase-TransitionsJournal of the American Chemical Society, 2012
- Survey and qualification of internal standards for quantification by 1H NMR spectroscopyJournal of Pharmaceutical and Biomedical Analysis, 2010
- Trioctylphosphine as Both Solvent and Stabilizer to Synthesize CdS NanorodsNanoscale Research Letters, 2009
- High Yield of Germanium Nanocrystals Synthesized from Germanium Diiodide in SolutionChemistry of Materials, 2005
- Efficient iterative schemes forab initiototal-energy calculations using a plane-wave basis setPhysical Review B, 1996
- Ab initiomolecular dynamics for open-shell transition metalsPhysical Review B, 1993