Ti3C2Tx MXene Thin Films and Intercalated Species Characterized by IR-to-UV Broadband Ellipsometry

MXenes are two-dimensional (2D) materials with versatile applications in optoelectronics, batteries, and catalysis. To unlock their full potential, it is crucial to characterize MXene interfaces and intercalated species in more detail than is currently possible with conventional optical spectroscopies. Here, we combine ultra-broadband ellipsometry and transmission spectroscopy from the mid-infrared (IR) to the deep-ultraviolet (UV) to probe quantitatively the composition, structure, transport, and optical properties of spray-coated Ti3C3Tx MXene thin films with varying material properties. We find film thickness heterogeneity and surface roughness in the low-nanometer range as well as depth-dependent conductivity properties, which we quantify with a graded Drude model. The optically determined sheet resistance is confirmed by four-point probe measurements. Furthermore, we employ density-functional-theory calculations to assign the observed absorption bands in the MXene dielectric function to various interband transitions from mixed MXene surface terminations. The prominent 1.48 eV (833 nm) spectral feature is found to be related to oxygen termination. Additional plasmonic effects are also suggested. Finally, we leverage the chemical sensitivity of state-of-the-art IR ellipsometry to separate the fingerprints of intercalated species within the MXene from the dominant Drude contributions, presenting for the first time a set of infrared optical constants of intercalated water. This work lays the foundation for optical metrology for interface engineering of MXene and other 2D materials.