ChemPhysChem p. 2647 - 2656 (2019)
Update date:2022-08-12
Topics:
Boote, Brett W.
Andaraarachchi, Himashi P.
Rosales, Bryan A.
Blome-Fernández, Rafael
Zhu, Feng
Reichert, Malinda D.
Santra, Kalyan
Li, Jingzhe
Petrich, Jacob W.
Vela, Javier
Smith, Emily A.
Lead halide perovskites possess unique characteristics that are well-suited for optoelectronic and energy capture devices, however, concerns about their long-term stability remain. Limited stability is often linked to the methylammonium cation, and all-inorganic CsPbX3 (X=Cl, Br, I) perovskite nanocrystals have been reported with improved stability. In this work, the photostability and thermal stability properties of CsPbX3 (X=Cl, Br, I) nanocrystals were investigated by means of electron microscopy, X-ray diffraction, thermogravimetric analysis coupled with FTIR (TGA-FTIR), ensemble and single particle spectral characterization. CsPbBr3 was found to be stable under 1-sun illumination for 16 h in ambient conditions, although single crystal luminescence analysis after illumination using a solar simulator indicates that the luminescence states are changing over time. CsPbBr3 was also stable to heating to 250 °C. Large CsPbI3 crystals (34±5 nm) were shown to be the least stable composition under the same conditions as both XRD reflections and Raman bands diminish under irradiation; and with heating the γ (black) phase reverts to the non-luminescent δ phase. Smaller CsPbI3 nanocrystals (14±2 nm) purified by a different washing strategy exhibited improved photostability with no evidence of crystal growth but were still thermally unstable. Both CsPbCl3 and CsPbBr3 show crystal growth under irradiation or heat, likely with a preferential orientation based on XRD patterns. TGA-FTIR revealed nanocrystal mass loss was only from liberation and subsequent degradation of surface ligands. Encapsulation or other protective strategies should be employed for long-term stability of these materials under conditions of high irradiance or temperature.
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