The top-down synthesis of single-layered Cs₄CuSb₂Cl₁₂ halide perovskite nanocrystals for photoelectrochemical...

The development of an all-inorganic lead-free perovskite nanocrystal is of crucial importance to solve the instability and lead toxicity of organic-inorganic lead hybrid perovskites. Herein, single-layered Cs4CuSb2Cl12 nanocrystals (NCs) with a narrow band gap of 1.6 eV were prepared for the first time via an ultrasonic exfoliation technique. This powerful top-down method was further generalized to synthesize a class of lead-free perovskite (Cs3Bi2X9 and Cs3Sb2X9) NCs. The experimental and theoretical studies revealed that not only inter-layer van der Waals forces but also in-plane chemical bonds played a critical role in the exfoliation process. Specifically, smaller uniform-sized NCs were observed for Cs4CuSb2Cl12 (∼3 nm) as compared to those for Cs3Sb2Cl9 (∼20 nm) although both Cs4CuSb2Cl12 and Cs3Sb2Cl9 exhibited a similar exfoliation energy (∼0.310 J m-2). This can be ascribed to the weaker in-plane chemical bonds of Cu-Cl (2.808 Å) and Sb-Cl (2.924 Å) in Cs4CuSb2Cl12 than the uniform Cl-Sb bond (2.69 Å) in Cs3Sb2Cl9 that allow for an easier exfoliation process. In addition, exfoliation of the Cs4CuSb2Cl12 microcrystal into NCs results in an indirect-to-direct bandgap transition and a reduced electron effective mass, which provides a rapid and steady photoelectrochemical response, demonstrating that Cs4CuSb2Cl12 NCs are a promising candidate for optoelectronic applications.