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Chalcogenide perovskites have attracted increasing research attention in recent years due to their promise of unique optoelectronic properties combined with stability. However, the synthesis and processing of these materials has been constrained by the need for high temperatures and/or long reaction times. In this work, we address the open question of a low-temperature growth mechanism for BaZrS 3 . Ultimately, a liquid-assisted growth mechanism for BaZrS 3 using molten BaS 3 as a flux is demonstrated at temperatures ≥540 °C in as little as 5 min. The role of Zr-precursor reactivity and S ( g .) on the growth mechanism and the formation of Ba 3 Zr 2 S 7 is discussed, in addition to the purification of resulting products using a straightforward H 2 O wash. The extension of this growth mechanism to other Ba-based chalcogenides is shown, including BaHfS 3, BaNbS 3, and BaTiS 3 . In addition, an alternative vapor-transport growth mechanism is presented using S 2 Cl 2 for the growth of BaZrS 3 at temperatures as low as 500 °C in at least 3 h. These results demonstrate the feasibility of scalable processing for the formation of chalcogenide perovskite thin-films.
Yang et al. (Tue,) studied this question.