Dismantling the "Red Wall" of Colloidal Perovskites: Highly Luminescent Formamidinium and Formamidinium-Cesium Lead Iodide Nanocrystals.

Title Dismantling the "Red Wall" of Colloidal Perovskites: Highly Luminescent Formamidinium and Formamidinium-Cesium Lead Iodide Nanocrystals.
Authors L. Protesescu; S. Yakunin; S. Kumar; J. Bär; F. Bertolotti; N. Masciocchi; A. Guagliardi; M. Grotevent; I. Shorubalko; M.I. Bodnarchuk; C.J. Shih; M.V. Kovalenko
Journal ACS Nano
DOI 10.1021/acsnano.7b00116
Abstract

Colloidal nanocrystals (NCs) of APbX3-type lead halide perovskites [A=Cs+, CH3NH3+ (methylammonium or MA+) or CH(NH2)2+ (formamidinium or FA+); X=Cl-, Br-, I-] have recently emerged as highly versatile photonic sources for applications ranging from simple photoluminescence down-conversion (e.g., for display backlighting) to light emitting diodes. From the perspective of spectral coverage, a formidable challenge facing the use of these materials is how to obtain stable emissions in the red and infrared spectral regions covered by the iodide-based compositions. So far, red-emissive CsPbI3 NCs have been shown to suffer from a delayed phase-transformation into a non-luminescent, wide-bandgap 1D polymorph, and MAPbI3 exhibits very limited chemical durability. In this work, we report a facile colloidal synthesis method for obtaining FAPbI3 and FA-doped CsPbI3 NCs that are uniform in size (10-15 nm), nearly cubic in shape and exhibit drastically higher robustness than their MA- or Cs-only cousins with similar sizes and morphologies. Detailed structural analysis indicated that the FAPbI3 NCs had a cubic crystal structure while the FA0.1Cs0.9PbI3 NCs had a 3D orthorhombic structure that was isostructural to the structure of CsPbBr3 NCs. Bright photoluminescence (PL) with high quantum yield (QY>70%) spanning red (690 nm, FA0.1Cs0.9PbI3 NCs) and near-infrared (near-IR, ca. 780 nm, FAPbI3 NCs) regions was sustained for several months or more in both the colloidal state and in films. The peak PL wavelengths can be fine-tuned by using post-synthetic cation- and anion-exchange reactions. Amplified spontaneous emissions (ASE) with low thresholds of 28 µJ cm-2 and 7.5 µJ cm-2 were obtained from the films deposited from FA0.1Cs0.9PbI3 and FAPbI3 NCs, respectively. Furthermore, light emitting diodes (LEDs) with a high external quantum efficiency (EQE) of 2.3% were obtained by using FAPbI3 NCs.

Citation L. Protesescu; S. Yakunin; S. Kumar; J. Bär; F. Bertolotti; N. Masciocchi; A. Guagliardi; M. Grotevent; I. Shorubalko; M.I. Bodnarchuk; C.J. Shih; M.V. Kovalenko.Dismantling the "Red Wall" of Colloidal Perovskites: Highly Luminescent Formamidinium and Formamidinium-Cesium Lead Iodide Nanocrystals.. ACS Nano. 2017. doi:10.1021/acsnano.7b00116

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Lead

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Iodine

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