Unraveling the Impact of Halide Mixing on Perovskite Stability

• Published in: Journal of the American Chemical Society 2019-02, Vol.141 (8), p.3515-3523
• Main Authors: Hieulle, Jeremy, Wang, Xiaoming, Stecker, Collin, Son, Dae-Yong, Qiu, Longbin, Ohmann, Robin, Ono, Luis K, Mugarza, Aitor, Yan, Yanfa, Qi, Yabing
• Format: Article
• Language: English
• Subjects: anions; chlorine; density functional theory; halides; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; iodine; mixing; photovoltaic cells; scanning tunneling microscopy; spectroscopy
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/jacs.8b11210

Increasing the stability of perovskites is essential for their integration in commercial photovoltaic devices. Halide mixing is suggested as a powerful strategy toward stable perovskite materials. However, the stabilizing effect of the halides critically depends on their distribution in the mixed compound, a topic that is currently under intense debate. Here we successfully determine the exact location of the I and Cl anions in the  CH3NH3PbBr3–y I y and CH3NH3PbBr3–z Cl z mixed halide perovskite lattices and correlate it with the enhanced stability we find for the latter. By combining scanning tunneling microscopy and density functional theory, we predict that, for low ratios, iodine and chlorine incorporation have different effects on the electronic properties and stability of the CH3NH3PbBr3 perovskite material. In addition, we determine the optimal Cl incorporation ratio for stability increase without detrimental band gap modification, providing an important direction for the fabrication of stable perovskite devices. The increased material stability induced by chlorine incorporation is verified by performing photoelectron spectroscopy on a half-cell device architecture. Our findings provide an answer to the current debate on halide incorporation and demonstrate their direct influence on device stability.