Resolving Transient Electron-Phonon Coupling with Time-Resolved Spontaneous Raman Spectroscopy

Understanding the interaction of charge carriers with lattice vibrations in the quasi-equilibrium regime is crucial for semiconductor functionality. However, the structural signatures of these interactions are often too subtle for conventional ultrafast techniques to detect. We developed a time-resolved spontaneous Raman technique based on time-correlated single-photon counting to track the spectral response following photoexcitation, providing subwavenumber spectral resolution and a subnanosecond temporal resolution. Unlike traditional pump-probe schemes, our method utilizes a modulated continuous-wave probe to maintain high spectral resolution, enabling detection of low-frequency Raman shifts down to 10 cm-1. Applied to lightly boron-doped silicon, we resolve intra-valence band and inter-valence band electronic transitions. A coupled-mode analysis of transient phonon asymmetry, resulting from interference with the intervalence band transitions, reveals electron-phonon coupling parameters that directly relate to carrier recombination. By capturing these subtle dynamical shifts, we demonstrate that this platform offers a powerful probe for investigating electron-phonon interactions in long-lived excited states.