Tuning Anisotropic Optical Properties of Inorganic and Hybrid Organic-Inorganic MXenes via Topochemical Surface Modification.
basic_science · Level V
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- Record sourced from PubMed, PMID 42486856.
- Also identified by DOI 10.1021/acs.nanolett.6c03430.
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Abstract
Surface groups are central to the properties of MXenes, yet their role in optical anisotropy remains largely unexplored. Here, we use a topochemical route to synthesize single crystals of stacked Ti<sub>3</sub>C<sub>2</sub>Cl<sub>2</sub> and hybrid organic-inorganic MXenes (<i>h</i>-MXenes) with lateral sizes of 38-75 μm, rotational registry, and tunable interlayer spacing. Solid-state NMR spectroscopy shows that topochemical substitution generates mixed amido, imido, and hydride surface motifs, which modify the electronic structure of the Ti<sub>3</sub>C<sub>2</sub> inorganic core. Imaging spectroscopic ellipsometry with micron-scale spatial resolution enables reconstruction of the complex dielectric tensor of individual multilayer crystals. Ti<sub>3</sub>C<sub>2</sub>Cl<sub>2</sub> exhibits a type-II hyperbolicity above 930 nm, whereas <i>h</i>-MXenes do not display hyperbolicity within the measured 300-1700 nm window, instead showing reduced in-plane conductivity, suppressed out-of-plane light absorption, and a chain-length-dependent blue shift of a near-infrared absorption feature. These results demonstrate topochemical surface modification as a direct handle for engineering MXenes as surface-programmable optical media.