The far‐infrared (far‐IR) remains a relatively underexplored region of the electromagnetic spectrum extending roughly from 20 to 100 µm in free‐space wavelength. Research within this range has been restricted due to a lack of optical materials that can be optimized to reduce losses and increase sensitivity, as well as by the long free‐space wavelengths associated with this spectral region. Here the exceptionally broad Reststrahlen bands of two Hf‐based transition metal dichalcogenides (TMDs) that can support surface phonon polaritons (SPhPs) within the mid‐infrared (mid‐IR) into the terahertz (THz) are reported. In this vein, the IR transmission and reflectance spectra of hafnium disulfide (HfS2) and hafnium diselenide (HfSe2) flakes are measured and their corresponding dielectric functions are extracted. These exceptionally broad Reststrahlen bands (HfS2: 165 cm−1; HfSe2: 95 cm−1) dramatically exceed that of the more commonly explored molybdenum‐ (Mo) and tungsten‐ (W) based TMDs (≈5–10 cm−1), which results from the over sevenfold increase in the Born effective charge of the Hf‐containing compounds. This work therefore identifies a class of materials for nanophotonic and sensing applications in the mid‐ to far‐IR, such as deeply sub‐diffractional hyperbolic and polaritonic optical antennas, as is predicted via electromagnetic simulations using the extracted dielectric function.
Chemical bonding and Born charge in 1T-HfS2
Abstract We combine infrared absorption and Raman scattering spectroscopies to explore the properties of the heavy transition metal dichalcogenide 1T-HfS 2 . We employ the LO–TO splitting of the E u vibrational mode along with a reevaluation of mode mass, unit cell volume, and dielectric constant to reveal the Born effective charge. We find $${Z}_{{\rm{B}}}^{* }$$ Z B * = 5.3 e , in excellent agreement with complementary first-principles calculations. In addition to resolving the controversy over the nature of chemical bonding in this system, we decompose Born charge into polarizability and local charge. We find α = 5.07 Å 3 and Z * = 5.2 e , respectively. Polar displacement-induced charge transfer from sulfur p to hafnium d is responsible for the enhanced Born charge compared to the nominal 4+ in hafnium. 1T-HfS 2 is thus an ionic crystal with strong and dynamic covalent effects. Taken together, our work places the vibrational properties of 1T-HfS 2 on a firm foundation and opens the door to understanding the properties of tubes and sheets.
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- Award ID(s):
- 2011401
- NSF-PAR ID:
- 10228071
- Date Published:
- Journal Name:
- npj 2D Materials and Applications
- Volume:
- 5
- Issue:
- 1
- ISSN:
- 2397-7132
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1038/s41699-021-00226-z
