Radiative defects in chloride-activated CdSe thin films

Read the full article See related articles

Discuss this preprint

Start a discussion What are Sciety discussions?

Listed in

This article is not in any list yet, why not save it to one of your lists.
Log in to save this article

Abstract

Sub-gap recombination—not the intrinsic band structure—limits wide-gap Se-based chalcogenide devices, yet how chloride activation rewires radiative pathways has remained unclear. Here we show that a 30 min CdCl₂ anneal transforms evaporated CdSe from porous nanograins into dense micrometer-scale polycrystals and sharpens the optical band edge, reducing the Urbach energy from 85 to 17 meV at 300 K. Combining temperature- and fluence-dependent photoluminescence (PL), time-resolved PL and hyperspectral mapping with hybrid-DFT, we resolve three emissive channels and quantify their mechanisms. A near-edge band is excitonic at low temperature and becomes free-carrier emission above ∼120 K, with linewidth set by a ∼25 meV polar phonon. A sub-gap band at Eg–0.45 eV requires above-gap carriers and quenches with 0.16 eV. A broad ∼1.05 eV band is driven by both above- and below-gap photons, blue-shifts by ∼20 meV from 100–300 K and retains microsecond lifetimes at room temperature. Mapping links infrared emission to edge-rich microstructure where band-edge PL is dimmer, blue-shifted and broadened. Calculations are consistent with chlorine donors, a selenium-vacancy pathway for the sub-gap band, and a cadmium-vacancy–chlorine complex for the infrared band, pointing to concrete routes to suppress sub-gap loss in chalcogenide wide-gap photovoltaics and detectors.

Article activity feed