Effect of calcium deposition on the surfaces of <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:msub> <mml:mi>WSe</mml:mi> <mml:mn>2</mml:mn> </mml:msub>
Functionalization of 2D materials and of transition metal dichalcogenides (TMDs) in particular is central for next generation devices and other applications. Here we study the effect of calcium dosing on the surfaces of clean WSe 2 and WS 2 in ultrahigh vacuum by x-ray photoelectron spectroscopy, low energy electron diffraction, and scanning electron microscopy. We find that Ca reacts with the chalcogens to CaSe x or CaS x and reduces the remaining tungsten. Ca forms an overlayer on top and causes an outdiffusion of the chalcogen. The overlayer oxidizes easily. We obtained detailed understanding of the interactions of archetypal TMD with an abundant alkali-earth element, which expands our knowledge of metal-surface interactions and of surface manipulation of 2D materials.