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Twist-engineering of the electronic structure in van-der-Waals layered materials relies predominantly on band hybridization between layers. Band-edge states in transition-metal-dichalcogenide semiconductors are localized around the metal atoms at the center of the three-atom layer and are therefore not particularly susceptible to twisting. Here, we report that high-lying excitons in bilayer WSe2 can be tuned over 235 meV by twisting, with a twist-angle susceptibility of 8.1 meV/°, an order of magnitude larger than that of the band-edge A-exciton. This tunability arises because the electronic states associated with upper conduction bands delocalize into the chalcogenide atoms. The effect gives control over excitonic quantum interference, revealed in selective activation and deactivation of electromagnetically induced transparency (EIT) in second-harmonic generation. Such a degree of freedom does not exist in conventional dilute atomic-gas systems, where EIT was originally established, and allows us to shape the frequency dependence, i.e., the dispersion, of the optical nonlinearity., Here, the authors report on the large twist-angle susceptibility of excitons involving upper conduction bands in transition metal dichalcogenide bilayers. These high-lying excitons couple with band-edge excitons, and give rise to nonlinear quantum-optical processes that become tuneable by twisting.

Underpotential deposition offers a predominant way to tailor the electronic structure of the catalytic surface at the atomic level, which is key to engineering materials with a high activity for (electro)catalysis. However, it remains challenging to precisely control and directly probe the underpotential deposition of a (sub)monolayer of atoms on nanoparticle surfaces. In this work, we in situ observe silver electrodeposited on gold nanocrystals surface from sub-monolayer to one monolayer by designing a highly sensitive electrochemical dark field scattering setup. The spectral variation is used to reconstruct the optical “cyclic voltammogram” of every single nanocrystal for understanding the underpotential deposition process on nanocrystals, which cannot be achieved by any other methods but are essential for creating novel nanomaterials., Underpotential deposition (UPD) is important to modify the surface properties of nanocrystals. Here, the authors show the application of in situ electrochemical dark field spectroscopy in identifying the UPD processes of silver on different facets of gold nanocrystals at the single nanoparticle level.