Abstract Electron–phonon coupling is fundamental to condensed-matter physics, governing various physical phenomena and properties in both conventional and quantum materials. Here we propose and demonstrate two-dimensional electron–phonon coupling spectroscopy that can directly extract the electron–phonon coupling matrix elements for specific phonon modes and different electron energies. Using this technique, we measure the electron energy dependence of the electron–phonon coupling strength for individual phonon modes. It allows us to identify distinct signatures distinguishing non-local Su–Schrieffer–Heeger-type couplings from local Holstein-type couplings. Applying this methodology to a methylammonium lead iodide perovskite, we reveal particularly different properties, for example, temperature dependence or anisotropy, of the electron–phonon couplings of two pronounced phonon modes. Our approach provides insights into the microscopic origin of the electron–phonon coupling and has potential applications in phonon-mediated ultrafast control material properties.

Phonon dynamics are a critical factor to control the optical properties of excited states in light-emitting materials. Here, we report an extremely slow relaxation of photoexcited lattice vibrations enabled by assembling the donor-acceptor (D-A) molecules [2-(9,9-dimethylacridin-10(9H)-yl)-9,9-dimethyl-9H-thioxanthene 10,10-dioxide], namely AC molecules, into dipolar crystal. By using photoexcitation-modulated Raman spectroscopy, we find that the crystalline-lattice vibrations monitored by Raman-scattering laser beam of 785 nm demonstrate an un-usual slow relaxation in the time scale of seconds after ceasing photoexcitation beam of 343 nm in such dipolar crystal. This presents extremely slow phonon dynamics enabled by crystalline-assembling the D-A molecules into a dipolar crystal. Simultaneously, the photoluminescence (PL) exhibits a prolonged behavior, lasting 10 ms after ceasing photoexcitation in dipolar AC crystal. This phenomenon provides an experimental hypothesis that the slow phonon dynamics function as an important mechanism to unusually prolong excited states dynamics upon crystalline-assembling the D-A molecules into dipolar crystal. This hypothesis can be verified by directly suppressing the phonon dynamics through freezing D-A molecular liquid into dipolar crystalline solid at 77 K to largely prolong the PL to 1 s- after removing photoexcitation. Clearly, crystalline-assembling D-A molecules provide the necessary conditions to enable slow phonon dynamics toward prolonging excited states dynamics.