Quantum-confined bismuth iodide perovskite nanocrystals in mesoporous matrices

Bismuth iodide perovskite nanocrystals are considered a viable alternative to the Pb halide ones due to their reduced toxicity and increased stability. However, it is still challenging to fabricate nanocrystals with a small and controlled size, and their electronic properties are not well understood. Here, we propose the growth of Bi iodide perovskite nanocrystals using different mesoporous silica with ordered pores of controlled diameter as templates. We obtain a series of confined Cs 3 Bi 2 I 9 and MA 3 Bi 2 I 9 perovskites with diameters of 2.3, 3.7, 7.4, and 9.2 nm, and precise size control. The complex absorption spectra of the encapsulated perovskites cannot be properly fitted using classical Tauc or Elliott formalisms. By fitting the spectra with a modified Elliott formula, the bandgap values and exciton binding energies (70-400 meV) could be extracted. The calculated bandgaps scale with the pore sizes. Using a combined experimental and theoretical approach, we demonstrate for the first time quantum confinement in 0D Bi-iodide perovskite nanocrystals. Encapsulation of bismuth iodide perovskites within the ordered silica pores of various diameters results is quantum-confined nanocrystals.