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1. Structural phase purification of bulk HfO 2 :Y through pressure cycling

   https://doi.org/10.1073/pnas.2312571121  

   Musfeldt, J. L. ; Singh, Sobhit ; Fan, Shiyu ; Gu, Yanhong ; Xu, Xianghan ; Cheong, S.-W. ; Liu, Z. ; Vanderbilt, David ; Rabe, Karin M. ( January 2024 , Proceedings of the National Academy of Sciences)

   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${}_2$.

    

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2. Intermediate valence state in YbB 4 revealed by resonant x-ray emission spectroscopy

   https://doi.org/10.1088/1361-648X/ac7629  

   Frontini, Felix ; Lebert, Blair W. ; Cho, K. K. ; Song, M. S. ; Cho, B. K. ; Pollock, Christopher J. ; Kim, Young-June ( June 2022 , Journal of Physics: Condensed Matter)

   We report the temperature dependence of the Yb valence in the geometrically frustrated compound${\mathrm{Y}\mathrm{b}\mathrm{B}}_4$from 12 to 300 K using resonant x-ray emission spectroscopy at the Yb$L_{{\alpha }_1}$transition. We find that the Yb valence,v, is hybridized between thev = 2 andv = 3 valence states, increasing from$v=2.61\pm 0.01$at 12 K to$v=2.67\pm 0.01$at 300 K, confirming that${\mathrm{Y}\mathrm{b}\mathrm{B}}_4$is a Kondo system in the intermediate valence regime. This result indicates that the Kondo interaction in${\mathrm{Y}\mathrm{b}\mathrm{B}}_4$is substantial, and is likely to be the reason why${\mathrm{Y}\mathrm{b}\mathrm{B}}_4$does not order magnetically at low temperature, rather than this being an effect of geometric frustration. Furthermore, the zero-point valence of the system is extracted from our data and compared with other Kondo lattice systems. The zero-point valence seems to be weakly dependent on the Kondo temperature scale, but not on the valence change temperature scaleT_v.

    

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3. Optical signatures of Dirac nodal lines in NbAs 2

   https://doi.org/10.1073/pnas.1809631115  

   Shao, Yinming ; Sun, Zhiyuan ; Wang, Ying ; Xu, Chenchao ; Sankar, Raman ; Breindel, Alexander J. ; Cao, Chao ; Fogler, Michael M. ; Millis, Andrew J. ; Chou, Fangcheng ; et al ( January 2019 , Proceedings of the National Academy of Sciences)

   Using polarized optical and magneto-optical spectroscopy, we have demonstrated universal aspects of electrodynamics associated with Dirac nodal lines that are found in several classes of unconventional intermetallic compounds. We investigated anisotropic electrodynamics of${\mathrm{N}\mathrm{b}\mathrm{A}\mathrm{s}}_2$where the spin-orbit coupling (SOC) triggers energy gaps along the nodal lines. These gaps manifest as sharp steps in the optical conductivity spectra${\sigma }_1\left(\omega \right)$. This behavior is followed by the linear power-law scaling of${\sigma }_1\left(\omega \right)$at higher frequencies, consistent with our theoretical analysis for dispersive Dirac nodal lines. Magneto-optics data affirm the dominant role of nodal lines in the electrodynamics of${\mathrm{N}\mathrm{b}\mathrm{A}\mathrm{s}}_2$.

    

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4. Large H 2 O solubility in dense silica and its implications for the interiors of water-rich planets

   https://doi.org/10.1073/pnas.1917448117  

   Nisr, Carole ; Chen, Huawei ; Leinenweber, Kurt ; Chizmeshya, Andrew ; Prakapenka, Vitali B. ; Prescher, Clemens ; Tkachev, Sergey N. ; Meng, Yue ; Liu, Zhenxian ; Shim, Sang-Heon ( April 2020 , Proceedings of the National Academy of Sciences)

   Sub-Neptunes are common among the discovered exoplanets. However, lack of knowledge on the state of matter in${\mathrm{H}}_2$O-rich setting at high pressures and temperatures ($P-T$) places important limitations on our understanding of this planet type. We have conducted experiments for reactions between${\mathrm{S}\mathrm{i}\mathrm{O}}_2$and${\mathrm{H}}_2$O as archetypal materials for rock and ice, respectively, at high$P-T$. We found anomalously expanded volumes of dense silica (up to 4%) recovered from hydrothermal synthesis above ∼24 GPa where the${\mathrm{C}\mathrm{a}\mathrm{C}\mathrm{l}}_2$-type (Ct) structure appears at lower pressures than in the anhydrous system. Infrared spectroscopy identified strong OH modes from the dense silica samples. Both previous experiments and our density functional theory calculations support up to 0.48 hydrogen atoms per formula unit of (${\mathrm{S}\mathrm{i}}_{1-x}{\mathrm{H}}_{4x}$)${\mathrm{O}}_2\hspace{0.17em}\left(x=0.12\right)$. At pressures above 60 GPa,${\mathrm{H}}_2$O further changes the structural behavior of silica, stabilizing a niccolite-type structure, which is unquenchable. From unit-cell volume and phase equilibrium considerations, we infer that the niccolite-type phase may contain H with an amount at least comparable with or higher than that of the Ct phase. Our results suggest that the phases containing both hydrogen and lithophile elements could be the dominant materials in the interiors of water-rich planets. Even for fully layered cases, the large mutual solubility could make the boundary between rock and ice layers fuzzy. Therefore, the physical properties of the new phases that we report here would be important for understanding dynamics, geochemical cycle, and dynamo generation in water-rich planets.

    

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5. Tuning metal/superconductor to insulator/superconductor coupling via control of proximity enhancement between NbSe 2 monolayers

   https://doi.org/10.1088/1361-648X/acbf92  

   Chiatti, Olivio ; Mihov, Klara ; Griffin, Theodor U. ; Grosse, Corinna ; Alemayehu, Matti B. ; Hite, Kyle ; Hamann, Danielle ; Mogilatenko, Anna ; Johnson, David C. ; Fischer, Saskia F. ( March 2023 , Journal of Physics: Condensed Matter)

   The interplay between charge transfer and electronic disorder in transition-metal dichalcogenide multilayers gives rise to superconductive coupling driven by proximity enhancement, tunneling and superconducting fluctuations, of a yet unwieldy variety. Artificial spacer layers introduced with atomic precision change the density of states by charge transfer. Here, we tune the superconductive coupling between$\text{NbS}{\text{e}}_{\text{2}}$monolayers from proximity-enhanced to tunneling-dominated. We correlate normal and superconducting properties in${\left[{\left(\text{SnSe}\right)}_{1+\delta }\right]}_m{\left[\text{NbS}{\text{e}}_{\text{2}}\right]}_1$tailored multilayers with varying SnSe layer thickness ($m=1-15$). From high-field magnetotransport the critical fields yield Ginzburg–Landau coherence lengths with an increase of$140\mathrm{\%}$cross-plane ($m=1-9$), trending towards two-dimensional superconductivity for$m>9$. We show cross-overs between three regimes: metallic with proximity-enhanced coupling ($m=1-4$), disordered-metallic with intermediate coupling ($m=5-9$) and insulating with Josephson tunneling ($m>9$). Our results demonstrate that stacking metal mono- and dichalcogenides allows to convert a metal/superconductor into an insulator/superconductor system, prospecting the control of two-dimensional superconductivity in embedded layers.

    

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