Alexander I. Tartakovskii

Bandstructure engineering using alloying is widely utilized for achieving optimized performance in modern semiconductor devices. While alloying has been studied in monolayer transition metal dichalcogenides, its application in van der Waals heterostructures built from atomically thin layers is largely unexplored. Here, heterobilayers made from monolayers of WSe 2 (or MoSe 2 ) and Mo x W 1 − x Se 2 alloy are fabricated and nontrivial tuning of the resultant bandstructure is observed as a function of concentration x . This evolution is monitored by measuring the energy of photoluminescence (PL) of the interlayer exciton (IX) composed of an electron and hole residing in different monolayers. In Mo x W 1 − x Se 2 /WSe 2 , a strong IX energy shift of ≈100 meV is observed for x varied from 1 to 0.6. However, for x < 0.6 this shift saturates and the IX PL energy asymptotically approaches that of the indirect bandgap in bilayer WSe 2 . This observation is theoretically interpreted as the strong variation of the conduction band K valley for x > 0.6, with IX PL arising from the K − K transition, while for x < 0.6, the bandstructure hybridization becomes prevalent leading to the dominating momentum‐indirect K − Q transition. This bandstructure hybridization is accompanied with strong modification of IX PL dynamics and nonlinear exciton properties. This work provides foundation for bandstructure engineering in van der Waals heterostructures highlighting the importance of hybridization effects and opening a way to devices with accurately tailored electronic properties.