Van der Waals SnSe2(1−x)S2x Alloys: Composition‐Dependent Bowing Coefficient and Electron–Phonon Interaction

The design of advanced functional materials with customized properties often requires the use of an alloy. This approach has been used for decades, but only recently to create van der Waals (vdW) alloys for applications in electronics, optoelectronics, and thermoelectrics. A route to engineering their physical properties is by mixing isoelectronic elements, as done for the SnSe_2(1?x)S_2x alloy. Here, by experiment and first‐principles modeling, it is shown that the value of x can be adjusted over a wide range, indicating good miscibility of the SnS₂ and SnSe₂ compounds. The x‐dependence of the indirect bandgap energy from E_ind = 1.20 eV for SnSe₂ to E_ind = 2.14 eV for SnS₂, corresponds to a large bowing coefficient b ≈ 1 eV, arising from volume deformation and charge exchange effects due to the different sizes and orbital energies of the S‐ and Se‐atoms. This also causes composition‐dependent phonon energy modes, electron–phonon interaction, and temperature dependence of E_ind. The alloys are exfoliable into thin layers with properties that depend on the composition, but only weakly on the layer thickness. This work shows that the electronic and vibrational properties of the SnSe_2(1?x)S_2x alloy and its thin layers provide a versatile platform for development and exploitation.