Ultralong Lifetime of Plasmon-Excited Electrons Realized in Nonepitaxial/Epitaxial Au@CdS/CsPbBr₃ Triple-Heteronanocrystals.

Abstract

Combination of the strong light-absorbing power of plasmonic metals with the superior charge carrier dynamics of halide perovskites is appealing for bio-inspired solar-energy conversion due to the potential to acquire long-lived plasmon-induced hot electrons. However, the direct coupling of these two materials, with Au/CsPbBr₃ heteronanocrystals (HNCs) as a prototype, results in severe suppression of plasmon resonances. The present work shows that interfacial engineering is a key knob for overcoming this impediment, based on the creation of a CdS mediate layer between Au and CsPbBr₃ forming atomically organized Au-CdS and CdS-CsPbBr₃ interfaces by nonepitaxial/epitaxial combined strategy. Transient spectroscopy studies demonstrate that the resulting Au@CdS/CsPbBr₃ HNCs generate remarkably long-lived plasmon-induced charge carriers with lifetime up to nanosecond timescale, which is several orders of magnitude longer than those reported for colloidal plasmonic metal-semiconductor systems. Such long-lived carriers extracted from plasmonic antennas enable to drive CO₂ photoreduction with efficiency outperforming previously reported CsPbBr₃ -based photocatalysts. The findings disclose a new paradigm for achieving much elongated time windows to harness the substantial energy of transient plasmons through realization of synergistic coupling of plasmonic metals and halide perovskites.