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We combine synchrotron-based infrared absorption and Raman scattering spectroscopies with diamond anvil cell techniques and first-principles calculations to explore the properties of hafnia under compression. We find that pressure drives HfO${}_2$:7%Y from the mixed monoclinic ($P{2}_1/c$)$+$antipolar orthorhombic ($\mathit{Pbca}$) phase to pure antipolar orthorhombic ($\mathit{Pbca}$) phase at approximately 6.3 GPa. This transformation is irreversible, meaning that upon release, the material is kinetically trapped in the$\mathit{Pbca}$metastable state at 300 K. Compression also drives polar orthorhombic ($Pca{2}_1$) hafnia into the tetragonal ($P{4}_2/nmc$) phase, although the latter is not metastable upon release. These results are unified by an analysis of the energy landscape. The fact that pressure allows us to stabilize targeted metastable structures with less Y stabilizer is important to preserving the flat phonon band physics of pure HfO${}_2$.

 

In order to explore the consequences of spin–orbit coupling on spin–phonon interactions in a set of chemically similar mixed metal oxides, we measured the infrared vibrational properties of Co4B2O9 (B = Nb, Ta) as a function of temperature and compared our findings with lattice dynamics calculations and several different models of spin–phonon coupling. Frequency vs temperature trends for the Co2+ shearing mode near 150 cm−1 reveal significant shifts across the magnetic ordering temperature that are especially large in relative terms. Bringing these results together and accounting for noncollinearity, we obtain spin–phonon coupling constants of −3.4 and −4.3 cm−1 for Co4Nb2O9 and the Ta analog, respectively. Analysis reveals that these coupling constants are derived from interlayer (rather than intralayer) exchange interactions and that the interlayer interactions contain competing antiferromagnetic and ferromagnetic contributions. At the same time, beyond-Heisenberg terms are minimized due to fortuitous symmetry considerations, different from most other 4d- and 5d-containing oxides. Comparison with other contemporary oxides shows that spin–phonon coupling in this family of materials is among the strongest ever reported, suggesting an origin for magnetoelectric coupling. 

Abstract Hafnia (HfO 2 ) is a promising material for emerging chip applications due to its high- κ dielectric behavior, suitability for negative capacitance heterostructures, scalable ferroelectricity, and silicon compatibility. The lattice dynamics along with phononic properties such as thermal conductivity, contraction, and heat capacity are under-explored, primarily due to the absence of high quality single crystals. Herein, we report the vibrational properties of a series of HfO 2 crystals stabilized with yttrium (chemical formula HfO 2 :  x Y, where x  = 20, 12, 11, 8, and 0%) and compare our findings with a symmetry analysis and lattice dynamics calculations. We untangle the effects of Y by testing our calculations against the measured Raman and infrared spectra of the cubic, antipolar orthorhombic, and monoclinic phases and then proceed to reveal the signature modes of polar orthorhombic hafnia. This work provides a spectroscopic fingerprint for several different phases of HfO 2 and paves the way for an analysis of mode contributions to high- κ dielectric and ferroelectric properties for chip technologies. 

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.