Lattice Dynamics and Electron–Phonon Coupling in Lead-Free Cs2AgIn1–xBixCl6 Double Perovskite Nanocrystals

Recently, lead free all-inorganic double perovskites have revolutionized photovoltaic research, showing promising light emitting efficiency and tunability via modification of inherent structural and chemical properties. Here, we report a combined experimental and theoretical study on the variation of carrier–lattice interaction and optoelectronic properties of Cs2AgIn1–xBixCl6 double perovskite nanocrystals with varying alloying concentrations. Our UV–vis study confirms the parity allowed first direct transition for x ≤ 0.25. Using a careful analysis of Raman spectra assisted with first-principles simulations, we assign the possible three types of active modes to intrinsic atomic vibrations; 2 T2g modes (one for translational motion of “Cs” and other for octahedral breathing), 1 Eg and 1 A1g mode for various stretching of Ag–Cl octahedra. Ab-initio simulation reveals dominant carrier-phonon scattering via Fröhlich mechanism near room temperature, with longitudinal optical phonons being effectively activated around 230 K. We observe a noticeable increase in hole mobility (∼4 times) with small Bi alloying, attributed to valence band (VB) maxima acquiring Bi-s orbital characteristics, thus resulting in a dispersive VB. We believe that our results should help to gain a better understanding of the intrinsic electronic and lattice dynamical properties of these compounds and provide a base toward improving the overall performance of double perovskite nanocrystals.