Light Absorption and Emission Dominated by Trions in the Type‑I van der Waals Heterostructures

van der Waals (vdW) heterostructures provide a powerful method to control the alignment of energy bands of atomically thin 2D materials. Under light illumination, the optical responses are dominated by Coulomb-bound electron–hole quasiparticles, for example, excitons, trions, and biexcitons, whose contributions accordingly depend on the types of heterostructures. For type-II heterostructures, it has been well established that light excitation results in electrons and holes that are separated in different layers, and the radiative recombination is dominated by the interlayer excitons. On the contrary, little is known about the corresponding optical responses of type-I cases. Understanding the optical characteristics of type-I heterostructures is important to the full exploration of the quasiparticle physics of the 2D heterostacks. In this study, we performed optical spectroscopy on type-I vdW heterostacks composed of monolayer MoTe2 and WSe2. Photoluminescence and reflection contrast spectroscopy show that the light absorption and emission are dominated by the Coulomb-bound trions. Importantly, we observed that the MoTe2 trion emission gets stronger compared with the exciton emission under resonant light excitation to the WSe2 trion absorption state, especially in the WSe2/MoTe2/WSe2 heterotrilayer. A detailed study of photoluminescence excitation further reveals that the charge-transfer mechanism is likely responsible for our observation, which differs from the exciton-dominated dipole–dipole energy transfer in type-II structures. Our demonstration implies that the type-I vdW heterostack provides new opportunities to engineer the light–matter interactions through many-body Coulomb-bound states.