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1. What happens when transition metal trichalcogenides are interfaced with gold?

   https://doi.org/10.1557/s43578-022-00744-6  

   Dhingra, Archit; Nikonov, Dmitri E.; Lipatov, Alexey; Sinitskii, Alexander; Dowben, Peter A. (September 2022, Journal of Materials Research)

   Abstract Transition metal trichalcogenides (TMTs) are two-dimensional (2D) systems with quasi-one-dimensional (quasi-1D) chains. These 2D materials are less susceptible to undesirable edge defects, which enhances their promise for low-dimensional optical and electronic device applications. However, so far, the performance of 2D devices based on TMTs has been hampered by contact-related issues. Therefore, in this review, a diligent effort has been made to both elucidate and summarize the interfacial interactions between gold and various TMTs, namely, In₄Se₃, TiS₃, ZrS₃, HfS₃, and HfSe₃. X-ray photoemission spectroscopy data, supported by the results of electrical transport measurements, provide insights into the nature of interactions at the Au/In₄Se₃, Au/TiS₃, Au/ZrS₃, Au/HfS₃, and Au/HfSe₃interfaces. This may help identify and pave a path toward resolving the contemporary contact-related problems that have plagued the performance of TMT-based nanodevices. Graphical abstract I–Vcharacteristics of (a) TiS3, (b) ZrS3, and (c) HfS3 

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2. Effect of Au/HfS ₃ interfacial interactions on properties of HfS ₃ -based devices

   https://doi.org/10.1039/d2cp01254e  

   Dhingra, Archit; Lipatov, Alexey; Loes, Michael J.; Abourahma, Jehad; Pink, Maren; Sinitskii, Alexander; Dowben, Peter A. (June 2022, Physical Chemistry Chemical Physics)

   X-ray photoemission spectroscopy (XPS) has been used to examine the interaction between Au and HfS 3 at the Au/HfS 3 interface. XPS measurements reveal dissociative chemisorption of O 2 , leading to the formation of an oxide of Hf at the surface of HfS 3 . This surface hafnium oxide, along with the weakly chemisorbed molecular species, such as O 2 and H 2 O, are likely responsible for the observed p-type characteristics of HfS 3 reported elsewhere. HfS 3 devices exhibit n-type behaviour if measured in vacuum but turn p-type in air. Au thickness-dependent XPS measurements provide clear evidence of band bending as the S 2p and Hf 4f core-level peak binding energies for Au/HfS 3 are found to be shifted to higher binding energies. This band bending implies formation of a Schottky-barrier at the Au/HfS 3 interface, which explains the low measured charge carrier mobilities of HfS 3 -based devices. The transistor measurements presented herein also indicate the existence of a Schottky barrier, consistent with the XPS core-level binding energy shifts, and show that the bulk of HfS 3 is n-type. 

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3. Chemical bonding and Born charge in 1T-HfS2

   https://doi.org/10.1038/s41699-021-00226-z  

   Neal, S. N.; Li, S.; Birol, T.; Musfeldt, J. L. (December 2021, npj 2D Materials and Applications)

   null (Ed.)

   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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4. Mid‐ to Far‐Infrared Anisotropic Dielectric Function of HfS ₂ and HfSe ₂

   https://doi.org/10.1002/adom.202200933  

   Kowalski, Ryan_A; Nolen, Joshua_Ryan; Varnavides, Georgios; Silva, Sebastian_Mika; Allen, Jack_E; Ciccarino, Christopher_J; Juraschek, Dominik_M; Law, Stephanie; Narang, Prineha; Caldwell, Joshua_D (September 2022, Advanced Optical Materials)

   Abstract 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. 

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5. The Electronic Structure of Zirconium and Hafnium Monochalcogenides

   https://doi.org/10.1021/acs.jpca.5c05402  

   F_Romeu, João G; Joyner, Nickolas A; Kaye, Elliot; Peterson, Kirk A; Kawagoe, Thomas T; Stinson, Samantha L; Morse, Michael D; Dixon, David A (October 2025, The Journal of Physical Chemistry A)

   High-level ab initio CCSD(T) and spin-orbit icMRCI+Q calculations were used to predict potential energy curves (PECs) for the lowest-lying states of ZrO, ZrS, HfO, and HfS. The prediction of the ground state is basis set dependent at the icMRCI+Q level for ZrO and ZrS due to the small singlet-triplet splitting between the lowest 1Σ+ and 3Δ states. CCSD(T) with a spin orbit correction predicted the 1Σ+ ground state in agreement with experiment. New all-electron basis sets were developed for Hf to improve the results over those predicted by use of effective core potentials (ECPs) that subsume the 4f electrons into the definition of the core. The use of the new DK-4f basis sets rather than ECPs became more important for HfO and HfS where there is a lack of a good core-valence separation. icMRCI+Q, CCSD(T), and DFT calculations for the spectroscopic parameters of ZrO, ZrS, HfO, and HfS were benchmarked with available experimental data. Bond dissociation energies (BDEs) of these four systems were calculated at the Feller-Peterson-Dixon (FPD) level to be 762.1 (ZrO), 543.5 (ZrS), 803.8 (HfO), and 575.1 kJ/mol (HfS), in excellent agreement with experiment. The HfS BDE was remeasured using the R3PI method, providing an updated experimental measurement of D0(HfS) = 5.978 ± 0.002 eV = 576.8 ± 0.2 kJ/mol. This experimental value, combined with experimental measurements of the ionization energies of Hf and HfS, gives the cationic BDE of D0(Hf+-S) = 5.124 ± 0.002 eV = 494.4 ± 0.2 kJ/mol. 

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