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DOE OSTI · 3393573

Tuning Anisotropic Optical Properties of Inorganic and Hybrid Organic–Inorganic MXenes via Topochemical Surface Modification

Kim, Young-Hwan [University of Chicago, IL (United States)] (ORCID:0000000304531434)·Fang, Hui [University of Pennsylvania, Philadelphia, PA (United States)] (ORCID:0000000240241234)·Noh, Hanaul [Park Systems Inc., Santa Clara, CA (United States)]·Md. Shawon, Abu Rashed [Iowa State University, Ames, IA (United States); Ames Laboratory (AMES), Ames, IA (United States)]·Han, Sanguk [University of Pennsylvania, Philadelphia, PA (United States)]·Intriago, Daniel [University of Pennsylvania, Philadelphia, PA (United States)]·Zhang, Teng [Drexel University, Philadelphia, PA (United States)] (ORCID:0000000249390594)·Cavanagh, Ashley E. [Washington University in St. Louis, MO (United States)] (ORCID:0000000165181138)·Akbar, Gusaimas M. H. H. [Washington University in St. Louis, MO (United States)]·Lagunas, Francisco [Washington University in St. Louis, MO (United States)]·Gogotsi, Yury [Drexel University, Philadelphia, PA (United States)] (ORCID:0000000194234032)·Vojvodic, Aleksandra [University of Pennsylvania, Philadelphia, PA (United States)] (ORCID:0000000255846711)·Rossini, Aaron J. [Iowa State University, Ames, IA (United States); Ames Laboratory (AMES), Ames, IA (United States)] (ORCID:0000000216799203)·Fakhraai, Zahra [University of Pennsylvania, Philadelphia, PA (United States)] (ORCID:0000000205979882)·Talapin, Dmitri V. [University of Chicago, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000264148587)
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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 3 C 2 Cl 2 and hybrid organic–inorganic MXenes (h-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 3 C 2 inorganic core. Imaging spectroscopic ellipsometry with micron-scale spatial resolution enables reconstruction of the complex dielectric tensor of individual multilayer crystals. Ti 3 C 2 Cl 2 exhibits a type-II hyperbolicity above 930 nm, whereas h-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.

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Hybrid materialsInorganic carbon compoundsInsulatorsMXenesMagnetic propertiesNuclear magnetic resonance spectroscopyOptical propertiesSurface functionalizationTopochemical synthesisTwo dimensional materials

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Kim, Young-Hwan [University of Chicago, IL (United States)] (ORCID:0000000304531434), Fang, Hui [University of Pennsylvania, Philadelphia, PA (United States)] (ORCID:0000000240241234), Noh, Hanaul [Park Systems Inc., Santa Clara, CA (United States)], Md. Shawon, Abu Rashed [Iowa State University, Ames, IA (United States); Ames Laboratory (AMES), Ames, IA (United States)], Han, Sanguk [University of Pennsylvania, Philadelphia, PA (United States)], Intriago, Daniel [University of Pennsylvania, Philadelphia, PA (United States)], Zhang, Teng [Drexel University, Philadelphia, PA (United States)] (ORCID:0000000249390594), Cavanagh, Ashley E. [Washington University in St. Louis, MO (United States)] (ORCID:0000000165181138), Akbar, Gusaimas M. H. H. [Washington University in St. Louis, MO (United States)], Lagunas, Francisco [Washington University in St. Louis, MO (United States)], Gogotsi, Yury [Drexel University, Philadelphia, PA (United States)] (ORCID:0000000194234032), Vojvodic, Aleksandra [University of Pennsylvania, Philadelphia, PA (United States)] (ORCID:0000000255846711), Rossini, Aaron J. [Iowa State University, Ames, IA (United States); Ames Laboratory (AMES), Ames, IA (United States)] (ORCID:0000000216799203), Fakhraai, Zahra [University of Pennsylvania, Philadelphia, PA (United States)] (ORCID:0000000205979882), Talapin, Dmitri V. [University of Chicago, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000264148587). 2026-07-22. Tuning Anisotropic Optical Properties of Inorganic and Hybrid Organic–Inorganic MXenes via Topochemical Surface Modification. https://doi.org/10.1021/acs.nanolett.6c03430

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