Triiodide-Induced Band-Edge Reconstruction of a Lead-Free Perovskite-Derivative Hybrid for Strong Light Absorption

Bismuth-based
hybrid perovskites have recently attracted great
attention for their environmentally friendly processing, chemical
stability, and photoresponsive properties. However, most of the known
lead-free hybrids show wide band gaps (Eg > 1.9 eV) that afford weak visible-light absorption. Here, we
show
a newly conceptual design strategy of intercalating triiodide to decrease
the prototypic band gap by ca. ∼0.44 eV. A new hybrid semiconducting
material of (4-methylpiperidinium)4·I3·BiI6 (MP-T-BiI6), adopting
the zero-dimensional (0D) perovskite-like framework, was reconstructed
from its prototype of (4-methylpiperidinium)3Bi2I9 (MP-Bi2I9). It is noteworthy that MP-T-BiI6 has a narrow band gap of 1.58 eV, almost
comparable to that of CH3NH3PbI3 (∼1.5
eV), which reveals its potential as the highly efficient light absorber.
Importantly, its semiconducting properties were solidly confirmed
by notable hole mobility (∼12.8 cm2 V–1 s–1), charge-trap density (∼1.13 ×
1010 cm–3), and photoconductive behaviors.
Moreover, theoretical calculations further disclose that the I-5p
orbitals of triiodide induce the band-edge reconstruction and behave
as a new conduction-band minimum at the Brillouin zone center. This
work paves a potential pathway for the large and diverse family of
lead-free hybrids to compete with lead absorbers.