Impurities play an important role during recombination processes in semiconductors. Their important role is sharpened in atomically-thin transition-metal dichalcogenides whose two-dimensional character renders electrons and holes highly susceptible to localization caused by remote charged impurities. We study a multitude of phenomena that arise from the interaction of localized electrons with excitonic complexes. Emphasis is given to the amplification of the phonon-assisted recombination of biexcitons when it is mediated by localized electrons, showing that this mechanism can explain recent photoluminescence experiments in ML-WSe$_2$. In addition, the magnetic-field dependence of this mechanism is analyzed. The results of this work point to (i) an intriguing coupling between the longitudinal-optical and homopolar phonon modes that can further elucidate various experimental results, (ii) the physics behind a series of localization-induced optical transitions in tungsten-based materials, and (iii) the importance of localization centers in facilitating the creation of biexcitons and exciton-exciton annihilation processes.
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