Diverging Expressions of Anharmonicity in Halide Perovskites

• Published in: Advanced materials (Weinheim) 2022-04, Vol.34 (14), p.e2107932-n/a
• Main Authors: Cohen, Adi, Brenner, Thomas M., Klarbring, Johan, Sharma, Rituraj, Fabini, Douglas H., Korobko, Roman, Nayak, Pabitra K., Hellman, Olle, Yaffe, Omer
• Format: Article
• Language: English
• Subjects: Anharmonicity; Breakdown; Crystal structure; Dynamic structural analysis; halide perovskites; Materials science; Optoelectronics; Perovskites; semiconductors; structural dynamics; Temperature dependence
• ISSN: 0935-9648; 1521-4095; 1521-4095
• DOI: 10.1002/adma.202107932

Lead‐based halide perovskite crystals are shown to have strongly anharmonic structural dynamics. This behavior is important because it may be the origin of their exceptional photovoltaic properties. The double perovskite, Cs2AgBiBr6, has been recently studied as a lead‐free alternative for optoelectronic applications. However, it does not exhibit the excellent photovoltaic activity of the lead‐based halide perovskites. Therefore, to explore the correlation between the anharmonic structural dynamics and optoelectronic properties in lead‐based halide perovskites, the structural dynamics of Cs2AgBiBr6 are investigated and are compared to its lead‐based analog, CsPbBr3. Using temperature‐dependent Raman measurements, it is found that both materials are indeed strongly anharmonic. Nonetheless, the expression of their anharmonic behavior is markedly different. Cs2AgBiBr6 has well‐defined normal modes throughout the measured temperature range, while CsPbBr3 exhibits a complete breakdown of the normal‐mode picture above 200 K. It is suggested that the breakdown of the normal‐mode picture implies that the average crystal structure may not be a proper starting point to understand the electronic properties of the crystal. In addition to our main findings, an unreported phase of Cs2AgBiBr6 is also discovered below ≈37 K. Raman spectroscopy is used to compare the anharmonic expressions in the structural dynamics of two halide perovskites. In Cs2AgBiBr6, clear normal modes are observed in all measured temperatures. Contrary to this, the Raman spectrum of CsPbBr3 exhibits a breakdown of the normal‐mode picture above 200 K. Implications of these diverging behaviors on the electronic properties of the crystals is discussed.