Why Fe Doping Kills Photoluminescence in CsPbCl3 but Not in CsPbBr3: Role of Midgap Fe 3d States and Electron-Phonon Coupling

Abstract

Understanding the impact of transition-metal doping on the optoelectronic properties of halide perovskite nanocrystals is essential for their rational design in photonic applications. We establish the microscopic origin of photoluminescence (PL) quenching in Fe-doped CsPbCl3 using spin-polarized density functional theory calculations. The emergence of Fe 3d midgap states creates efficient electron-trapping centers that drive nonradiative recombination, accounting for the reduced PL intensity. Extending this analysis to Fe-doped CsPbX3 (X = Cl, Br), we show experimentally that although PL intensity is suppressed in both systems relative to their pristine counterparts, their high-doping behavior diverges: CsPbCl3 becomes completely non-emissive, whereas CsPbBr3 retains a finite, saturated PL intensity. Despite this contrast, electronic structure calculations reveal nearly identical midgap states in both materials, indicating that electronic effects alone cannot explain the distinct PL responses. Phonon calculations likewise fail to capture this difference. In contrast, electron-phonon coupling calculations based on the deformation potential approach reveal significantly stronger coupling in Fe-doped CsPbCl3, enabling efficient dissipation of electronic excitation energy into lattice vibrations and leading to complete PL quenching. These results identify electron-phonon coupling as the key factor governing halide-dependent PL quenching and provide a unified microscopic framework for dopant-induced nonradiative processes in halide perovskites.