Low pressure reversibly driving colossal barocaloric effect in two-dimensional vdW alkylammonium halides.

Plastic crystals as barocaloric materials exhibit the large entropy change rivalling freon, however, the limited pressure-sensitivity and large hysteresis of phase transition hinder the colossal barocaloric effect accomplished reversibly at low pressure. Here we report reversible colossal barocaloric effect at low pressure in two-dimensional van-der-Waals alkylammonium halides. Via introducing long carbon chains in ammonium halide plastic crystals, two-dimensional structure forms in (CH3-(CH2)n-1)2NH2X (X: halogen element) with weak interlayer van-der-Waals force, which dictates interlayer expansion as large as 13% and consequently volume change as much as 12% during phase transition. Such anisotropic expansion provides sufficient space for carbon chains to undergo dramatic conformation disordering, which induces colossal entropy change with large pressure-sensitivity and small hysteresis. The record reversible colossal barocaloric effect with entropy change ΔSr ~ 400 J kg-1 K-1 at 0.08 GPa and adiabatic temperature change ΔTr ~ 11 K at 0.1 GPa highlights the design of novel barocaloric materials by engineering the dimensionality of plastic crystals.

ANi5Bi5.6+δ (A = K, Rb, and Cs): Quasi-One-Dimensional Metals Featuring [Ni5Bi5.6+δ]- Double-Walled Column with Strong Diamagnetism.

A new series of compounds, ANi5Bi5.6+δ (where A = K, Rb, and Cs) are discovered with a quasi-one-dimensional (Q1D) [Ni5Bi5.6+δ]- double-walled column and a coaxial inner one-dimensional Bi atomic chain. The columns are linked to each other by intercolumn Bi-Bi bonds and separated by an A+ cation. Typical metallic behaviors with strong correlation of itinerant electrons and the Sommerfeld coefficient enhanced with the increasing cationic radius were experimentally observed and supported by first-principles calculations. Compared to AMn6Bi5 (where A = K, Rb, and Cs), the enhanced intercolumn distances and the substitution of Ni for Mn give rise to strong diamagnetic susceptibilities in ANi5Bi5.6+δ. First-principles calculations reveal possible uncharged Ni atoms with even number of electrons in ANi5Bi5.6+δ, which may explain the emergence of diamagnetism. ANi5Bi5.6+δ, as Q1D diamagnetic metals with strong electron correlation, provide a unique platform to understand exotic magnetism and explore novel quantum effects.

2D FeOCl: A Highly In-Plane Anisotropic Antiferromagnetic Semiconductor Synthesized via Temperature-Oscillation Chemical Vapor Transport.

2D van der Waals (vdW) transition-metal oxyhalides with low symmetry, novel magnetism, and good stability provide a versatile platform for conducting fundamental research and developing spintronics. Antiferromagnetic FeOCl has attracted significant interest owing to its unique semiconductor properties and relatively high Néel temperature. Herein, good-quality centimeter-scale FeOCl single crystals are controllably synthesized using the universal temperature-oscillation chemical vapor transport (TO-CVT) method. The crystal structure, bandgap, and anisotropic behavior of the 2D FeOCl are explored in detail. The absorption spectrum and electrical measurements reveal that 2D FeOCl is a semiconductor with an optical bandgap of ≈2.1 eV and a resistivity of ≈10-1  Ω m at 295 K, and the bandgap increases with decreasing thickness. Strong in-plane optical and electrical anisotropies are observed in 2D FeOCl flakes, and the maximum resistance anisotropic ratio reaches 2.66 at 295 K. Additionally, the lattice vibration modes are studied through temperature-dependent Raman spectra and first-principles density functional calculations. A significant decrease in the Raman frequencies below the Néel temperature is observed, which results from the strong spin-phonon coupling effect in 2D FeOCl. This study provides a high-quality low-symmetry vdW magnetic candidate for miniaturized spintronics.

Anisotropic terahertz dielectric responses of sodium nitrate crystals.

Terahertz (THz) spectroscopy has become an effective tool to characterize the low-frequency rotational and vibrational modes of molecules. In addition, novel THz dielectric responses and optical properties on the basis of molecular rotation and vibration have attracted lots of attention because of their potential application in THz devices. In this paper, the dielectric response of low-symmetric sodium nitrate crystals in the frequency range of 0.2-1.5 THz was experimentally demonstrated. Four absorption bands at 0.23, 0.47, 0.92, and 1.15 THz were observed in the dielectric spectra and were tentatively ascribed to the rotational motion of nitrate ions. Based on the molecular rotation mechanism, the dielectric anisotropy and dielectric resonance of the crystal were discussed in detail.