Two-Step Chemical Vapor Deposition-Synthesized Lead-Free All-Inorganic Cs₃Sb₂Br₉ Perovskite Microplates for Optoelectronic Applications

Abstract

Lead-based halide perovskites (APbX₃, where A = organic or inorganic cation, X = Cl, Br, I) are suitable materials for many optoelectronic devices due to their many attractive properties. However, the concern of lead toxicity and the poor ambient and operational stability of the organic cation group greatly limit their practical utilization. Therefore, there has recently been great interest in lead-free, environment-friendly all-inorganic halide perovskites (IHPs). Sb and Sn are common species suggested to replace Pb for Pb-free IHPs. However, the large difference in the melting points of the precursor materials (e.g., CsBr and SbBr₃ precursors for Cs₃Sb₂Br₉) makes the chemical vapor deposition (CVD) growth of high-quality Pb-free IHPs a very challenging task. In this work, we developed a two-step CVD method to overcome this challenge and successfully synthesized Pb-free Cs₃Sb₂Br₉ perovskite microplates. Cs₃Sb₂Br₉ microplates ∼25 μm in size with the exciton absorption peak at ∼2.8 eV and a band gap of ∼2.85 eV were obtained. The microplates have a smooth hexagonal morphology and show a large Stokes shift of ∼450 meV and exciton binding energy of ∼200 meV. To demonstrate the applications of these microplates in optoelectronics, simple photoconductive devices were fabricated. These photodetectors exhibit a current on/off ratio of 2.36 × 10², a responsivity of 36.9 mA/W, and a detectivity of 1.0 × 10¹⁰ Jones with a fast response of rise and decay time of 61.5 and 24 ms, respectively, upon 450 nm photon irradiation. Finally, the Cs₃Sb₂Br₉ microplates also show good stability in ambient air without encapsulation. These results demonstrate that the 2-step CVD process is an effective approach to synthesize high-quality all-inorganic lead-free Cs₃Sb₂Br₉ perovskite microplates that have the potential for future high-performance optoelectronic device applications.