Excitonic trion population in two-dimensional halide perovskites

There are many reports of a surprisingly high charge-carrier density with sizable mobility in photoexcited two-dimensional (2D) halide perovskites despite their unusually high exciton binding energy. In this work we study the thermodynamic quasiequilibrium of the relative population of photoexcited free quasielectron/quasihole pairs, neutral excitons, and excitonic trions, in 2D materials that support such excitonic complexes with large binding energy. We derive and solve the general Saha equations which describe the detailed balance of such a system of photoexcited electronic degrees of freedom forming a multicomponent fluid of excitations in thermodynamic quasiequilibrium. The solution to these equations, for the special case of 2D perovskites where the reported exciton and excitonic trion binding energies are of the order of 0.3--0.4 eV for the former and 30--40 meV for the latter, reveals that while the charge-neutral excitonic population dominates all other excitations, at room temperature and below, the excitonic trion component can be the dominant population among charge carriers. We also argue that trionic hopping can take place via a tunneling mechanism which is speculated to play a role in a novel charge-transport mechanism.