Abstract: The Sun may capture asymmetric dark matter (DM), which can subsequently form bound-states through the radiative emission of a sub-GeV scalar. This process enables generation of scalars without requiring DM annihilation. In addition to DM capture on nucleons, the DM-scalar coupling responsible for bound-state formation also induces capture from self-scatterings of ambient DM particles with DM particles already captured, as well as with DM bound-states formed in-situ within the Sun. This scenario is studied in detail by solving Boltzmann equations numerically and analytically. In particular, we take into consideration that the DM self-capture rates require a treatment beyond the conventional Born approximation. We show that, thanks to DM scatterings on bound-states, the number of DM particles captured increases exponentially, leading to enhanced emission of relativistic scalars through bound-state formation, whose final decay products could be observable. We explore phenomenological signatures with the example that the scalar mediator decays to neutrinos. We find that the neutrino flux emitted can be comparable to atmospheric neutrino fluxes within the range of energies below one hundred MeV. Future facilities like Hyper-K, and direct DM detection experiments can further test such scenario.