Chalcogen and halogen surface termination coverage in MXenes – structure, stability, and properties

Abstract MXenes are a diverse family of two-dimensional (2D) transition metal carbides, nitrides, and carbonitrides. They can be synthesized through both top-down approaches, such as selective etching of A-layers from MAX phases using acids or molten salts, and bottom-up approaches, such as direct synthesis using chemical vapor deposition. However, the degree of the surface termination coverage depends on the synthesis route and is one key parameter for controlling its properties. This study focuses on halogen and chalcogen terminated MXenes, particularly M2CTx where M = Ti, Zr, V, Nb, Ta, and T = S, Se, Te, Cl, Br, I, and with surface termination coverage ranging from 100% (ideal, x = 2) to 50% (x = 1). The incorporation of oxygen on vacant termination sites was also evaluated. Using density functional theory (DFT) calculations, we investigated the structural, electronic, and mechanical properties of these MXenes. Our findings reveal that non-ideal termination coverage (x < 2) is more favorable for MXenes terminated with a larger size of T, such as Ti2CBrx, Nb2CClx, and Ta2CClx, and leads to mixed termination sites and lower binding energies. A reduced binding energy may facilitate delamination into single sheets, however, too low termination coverage may also cause structural collapse. Electronic properties showed increased number of states at the Fermi level under non-ideal coverage, potentially enhancing the conductivity. Mechanically, we find the moduli of MXenes to be comparable to other 2D materials, such as transition metal chalcogenides and hexagonal boron nitride, indicating their suitability for applications requiring flexibility and durability. This study underscores the potential of tailoring MXene properties through precise control of termination coverage and composition, paving the way for enhanced application-specific performance.