Sulfur Adatom and Vacancy Accelerate Charge Recombination in MoS2 but by Different Mechanisms: Time-Domain Ab Initio Analysis

Two-dimensional transition metal dichalcogenides (TMDs) have appeared on the horizon of materials science and solid-state physics due to their unique properties and diverse applications. TMD performance depends strongly on material quality and defect morphology. Calculations predict that sulfur adatom and vacancy are among the most energetically favorable defects in MoS2 with vacancies frequently observed during chemical vapor deposition. By performing ab initio quantum dynamics calculations we demonstrate that both adatom and vacancy accelerate nonradiative charge carrier recombination but this happens through different mechanisms. Surprisingly, holes never significantly populate the shallow trap state created by the sulfur adatom because the trap is strongly localized and decoupled from free charges. Charge recombination bypasses the hole trap. Instead, it occurs directly between free electron and hole. The recombination is faster than in pristine MoS2 because the adatom strongly perturbs the MoS2 layer, breaks its symmetry, and allows more phonon modes to couple to the electronic subsystem. In contrast, the sulfur vacancy accelerates charge recombination by the traditional mechanism involving charge trapping, followed by recombination. This is because the hole and electron traps created by the vacancy are much less localized than the hole trap created by the adatom. Because the sulfur adatom accelerates charge recombination by a factor of 7.9, compared to 1.7 due to vacancy, sulfur adatoms should be strongly avoided. The generated insights highlight the diverse behavior of different types of defects, reveal unexpected features, and provide the mechanistic understanding of charge dynamics needed for tailoring TMD properties and building high-performance devices.