Solution Deposition for Chalcogenide Perovskites: A Low-Temperature Route to BaMS₃ Materials (M = Ti, Zr, Hf)

Abstract

Chalcogenide perovskites, including BaZrS3, have been suggested as highly stable alternatives to halide perovskites. However, the synthesis of chalcogenide perovskites has proven to be a significant challenge, often relying on excessively high temperatures and methods that are incompatible with device integration. In this study, we developed a solution-based approach to the deposition of BaZrS3. This method utilizes a combination of a soluble barium thiolate and nanoparticulate zirconium hydride. Following solution-based deposition of the precursors and subsequent sulfurization, BaZrS3 can be obtained at temperatures as low as 500 °C. Furthermore, this method was extended to other chalcogenide perovskite (BaHfS3) and perovskite-related (BaTiS3) materials.

Liquid Flux–Assisted Mechanism for Modest Temperature Synthesis of Large‐Grain BaZrS3 and BaHfS3 Chalcogenide Perovskites

“…Additionally, sharper photoluminescence has been obtained for BaHfS 3 compared to BaZrS 3 . [ 18 ] As BaHfS 3 also contains barium and sulfur, a liquid BaS x flux should also be applicable to its synthesis. While early reports on the synthesis of BaHfS 3 using binary sulfides utilized a temperature of 1100 °C for 48 h, [ 11 ] we observed that adding excess sulfur to powder precursors BaS and HfS 2 such that the Ba:Hf:S mole ratio is 1:1:9 brought the reaction conditions down to 575 °C and 12 h ( Figure a).…”

“…Our group recently developed a direct‐to‐film solution‐processed route for BaMS 3 (M = Ti, Zr, Hf) materials that utilizes heat treatment in a sulfur‐containing atmosphere at modest temperatures from 500 to 575 °C. [ 18 ] For the case of BaZrS 3 , large grains on the order of hundreds of nanometers were obtained, which is desirable for applications in thin‐film photovoltaics.…”

“…Our group recently developed a direct-tofilm solution-processed route for BaMS 3 (M = Ti, Zr, Hf ) materials that utilizes heat treatment in a sulfur-containing atmosphere at modest temperatures from 500 to 575 °C. [18] For the case of BaZrS 3 , large grains on the order of hundreds of nanometers were obtained, which is desirable for applications in thin-film photovoltaics.Large grain sizes achieved at modest temperatures and short reaction times are key features of liquid flux-assisted synthesis, which is prevalent in chalcogenide photovoltaic materials like Cu(In,Ga)(S,Se) 2 and Cu 2 ZnSn(S,Se) 4 . Hages et al showed that by heating a nanocrystalline Cu 2 ZnSnS 4 film in a…”

Synthesis of BaZrS3 and BaHfS3 Chalcogenide Perovskite Films Using Single‐Phase Molecular Precursors at Moderate Temperatures

“…As stated above, solution‐based synthesis of a large number of multinary chalcogenides, especially those based on Group 11–15 elements, are available [37, 49, 50] . However, until recently, solution‐based synthesis of multinary AMS 3 (A=Ca, Sr, Ba; M=Ti, Zr, Hf) compounds has been missing from the literature [46–48, 58] . Creutz Group reported an early synthesis of non‐perovskite BaTiS 3 nanorods using dithiocarbamate complexes of Ba and Ti in oleylamine [58] .…”

Recent progress in chalcogenide perovskites: toward low-temperature solution processing

“…[36] c. Chemical formular of the nanoparticle synthesis with DBuDTC. [37] 이재욱, 양우석 태로 기판 위에 도포하는 것에 성공하였다 [38] . 이 연구에…”