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Chalcogenide perovskites are promising semiconductor materials with attractive optoelectronic properties and appreciable stability, making them enticing candidates for photovoltaics and related electronic applications. Traditional synthesis methods for these materials have long suffered from high‐temperature requirements of 800–1000 °C. However, the recently developed solution processing route provides a way to circumvent this. By utilizing barium thiolate and ZrH2, this method is capable of synthesizing BaZrS3perovskite at modest temperatures (500–600 °C), generating crystalline domains on the order of hundreds of nanometers in size. Herein, a systematic study of this solution processing route is done to gain a mechanistic understanding of the process and to supplement the development of device quality fabrication methodologies. A barium polysulfide liquid flux is identified as playing a key role in the rapid synthesis of large‐grain BaZrS3perovskite at modest temperatures. Additionally, this mechanism is successfully extended to the related BaHfS3perovskite. The reported findings identify viable precursors, key temperature regimes, and reaction conditions that are likely to enable the large‐grain chalcogenide perovskite growth, essential toward the formation of device‐quality thin films.
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A Low-temperature Growth Mechanism for Chalcogenide Perovskites
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 BaZrS3. Ultimately, a liquid-assisted growth mechanism for BaZrS3 using molten BaS3 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 Ba3Zr2S7 is discussed, in addition to the purification of resulting products using a straightforward H2O wash. The extension of this growth mechanism to other Ba-based chalcogenides is shown, including BaHfS3, BaNbS3, and BaTiS3. In addition, an alternative vapor-transport growth mechanism is presented using S2Cl2 for the growth of BaZrS3 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. (DOI: 10.1021/acs.chemmater.3c00494)
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- PAR ID:
- 10420169
- Date Published:
- Journal Name:
- Chemistry of materials
- ISSN:
- 1520-5002
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acs.chemmater.3c00494
