Sublattice Distortion Enabled Strong Interplay between Phonon Vibrations, Electron-Phonon Coupling, and Self-Trapped Excitonic Emissions in Cs2Ag1-xNaxBiCl6 Double Perovskites

Sublattice distortion resulting from alloying compositionally distinct double perovskites is shown to influence photoluminescence emission in Cs2Ag1-xNaxBiCl6 (0 < x < 1). The end members show negligible photoluminescence, whereas interestingly the alloys exhibit broad photoluminescence. These emissions are attributed to self-trapped excitons (STE) resulting from sublattice distortions arising due to the mismatch in [AgCl6](5-) and [BiCl6](3-) octahedra. Change in sublattice distortions plays significant role in the formation and recombination of STEs. The STE emission intensity and quantum yield greatly depend on x, with highest intensity observed for x = 0.75, consistent with a large change in sublattice found at this x. Variation in photoluminescence properties with composition follows a similar trend as that of bandgap and phonon vibrational changes observed due to sublattice distortion. Temperature-dependent phonon vibrations and photoluminescence studies reveal a giant electron-phonon coupling. A strong synergy between STE emissions, electron-phonon coupling, bandgap, and phonon vibrations in double perovskites with sublattice distortions is demonstrated.

Automated summary

Sublattice distortion resulting from alloying compositionally distinct double perovskites affects the photoluminescence emission, mainly through the formation and recombination of self-trapped excitons (STE). The intensity and quantum yield of STE emission depend on the alloy composition, with the highest intensity observed at a specific composition due to a large change in sublattice distortion. The variation in photoluminescence properties follows a similar trend as that of bandgap and phonon vibrational changes caused by sublattice distortion.