Structural Evolution during Reversible Halogen Intercalation into WTe 2 : Commensurate-Incommensurate WTe 2 I and Multistage WTe 2 Br x (x = 0.5, 1.0 and 1.25)

Abstract

Halogen intercalation into the layered material tungsten ditelluride (WTe2) provides a unique pathway to tune its structural and electronic properties. In this study, we detail the synthesis and characterization of the new bromine-intercalated phases WTe2Brx (x = 0.5, 1.0, and 1.25), and reinvestigate the iodine-intercalated analogue, WTe2I. A defining feature of the bromine system is its rapid and reversible "breathing" behavior at room temperature, allowing guest molecules to be absorbed or released from the van der Waals gaps under ambient conditions. Structural analyses shows that the bromine-poor phase WTe2Br0.5 crystallizes in the orthorhombic space group Pmmn, thereby maintaining a uniform stacking sequence. In contrast, the bromine-rich WTe2Br1.25 phase (space group Imm2) adopts an architecture where two distinct types of bromine layers alternate between the host layers. For the iodine system, the compound WTe2I exhibits both incommensurate and commensurate (3+1)D modulated variants in the superspace group P21/m(α0γ)00. In the commensurate polytype, the structural modulation locks into a rational vector, q = (1/2, 0, 1/6), which can be described also as a 3D supercell. Electronic structure calculations show WTe2Br0.5 and commensurately modulated WTe2I to be metals with flat bands at the Fermi energy arisng from the intercalation. These findings demonstrate the unusual stability and structural flexibility of anionic intercalation in a transition metal dichal-cogenides.