Superstructures, Commensurations, and Rotation of Single-Layer TaS₂ on Au(111) Induced by Cs...

We use in situ synchrotron grazing incidence X-ray diffraction and X-ray reflectivity to investigate with high resolution the structure of a two-dimensional single layer of tantalum sulfide grown on a Au(111) surface and its evolution during intercalation by Cs atoms and deintercalation, which decouples and recouples the two materials, respectively. The grown single layer consists of a mixture of TaS₂ and its S-depleted version, TaS, both aligned with gold, and forming moirés where 7 (respectively 13) lattice constants of the 2D layer almost perfectly match 8 (respectively 15) substrate lattice constants. Intercalation fully decouples the system by lifting the single layer by ∼370 pm and induces an increase of its lattice parameter by 1-2 picometers. The system gradually evolves, during cycles of intercalation/deintercalation assisted by an H₂S atmosphere, toward a final coupled state consisting of the fully stoichiometric TaS₂ dichalcogenide whose moiré is found very close to the 7/8 commensurability. The reactive H₂S atmosphere appears necessary to achieve full deintercalation, presumably by preventing S depletion and the concomitant strong bonding with the intercalant. The structural quality of the layer improves during the cyclic treatment. In parallel, because they are decoupled from the substrate by the intercalation of cesium, some of the TaS₂ flakes rotate by 30°. These produce two additional superlattices with characteristic diffraction patterns of different origins. The first is aligned with gold's high symmetry crystallographic directions and is a commensurate moiré ((6 × 6)-Au(111) coinciding with (3√3 × 3√3)R30°-TaS₂). The second is incommensurate and corresponds to a near coincidence of (6 × 6) unit cells of 30°-rotated TaS₂ with (4√3 × 4√3)Au(111) surface ones. This structure, which is less coupled to gold, might be related to the ∼(3× 3) charge density wave previously reported even at room temperature in TaS₂ grown on noninteracting substrates. A (3 × 3) superstructure of 30°-rotated TaS₂ islands is indeed revealed by complementary scanning tunneling microscopy.