Giant Density of States Enhancement Driven by a Zero-Mode Landau Level in Semimetallic Black Phosphorus under Pressure.

Dirac fermion systems form a unique Landau level at the Fermi level-the so-called zero mode-whose observation itself will provide strong evidence of the presence of Dirac dispersions. Here, we report the study of semimetallic black phosphorus under pressure by ^{31}P-nuclear magnetic resonance measurements in a wide range of magnetic field up to 24.0 T. We have found a field-induced giant enhancement of 1/T_{1}T, where 1/T_{1} is the nuclear spin lattice relaxation rate: 1/T_{1}T at 24.0 T reaches more than 20 times larger than that at 2.0 T. The increase in 1/T_{1}T above 6.5 T is approximately proportional to the squared field, implying a linear relationship between the density of states and the field. We also found that, while 1/T_{1}T at a constant field is independent of temperature in the low-temperature region, it steeply increases with temperature above 100 K. All these phenomena are well explained by considering the effect of Landau quantization on three-dimensional Dirac fermions. The present study demonstrates that 1/T_{1} is an excellent quantity to probe the zero-mode Landau level and to identify the dimensionality of the Dirac fermion system.

Electronic structure of dense solid oxygen from insulator to metal investigated with X-ray Raman scattering.

Electronic structures of dense solid oxygen have been investigated up to 140 GPa with oxygen K-edge X-ray Raman scattering spectroscopy with the help of ab initio calculations based on density functional theory with semilocal metageneralized gradient approximation and nonlocal van der Waals density functionals. The present study demonstrates that the transition energies (Pi*, Sigma*, and the continuum) increase with compression, and the slopes of the pressure dependences then change at 94 GPa. The change in the slopes indicates that the electronic structure changes at the metallic transition. The change in the Pi* and Sigma* bands implies metallic characteristics of dense solid oxygen not only in the crystal a-b plane but also parallel to the c axis. The pressure evolution of the spectra also changes at ∼40 GPa. The experimental results are qualitatively reproduced in the calculations, indicating that dense solid oxygen transforms from insulator to metal via the semimetallic transition.

Structure refinement of black phosphorus under high pressure.

The structure refinement of black phosphorus was performed at pressures of up to 3.2 GPa at room temperature by powder neutron diffraction techniques. The bond lengths and bond angles between the phosphorus atoms at pressures were precisely determined and confirmed to be consistent with those of the previous single crystal x-ray analysis [A. Brown and S. Rundqvist, Acta Cryst. 19, 684 (1965)]. Although the lattice parameters exhibited an anisotropic compressibility, the covalent P1-P2 and P1-P3 bond lengths were almost independent of pressure and only the P3-P1-P2 bond angle was reduced significantly. On the basis of our results, the significant discrepancy in the bond length reported by Cartz et al. [J. Chem. Phys. 71, 1718 (1979)] has been resolved. Our structural data will contribute to the elucidation of the Dirac semimetal state of black phosphorus under high pressure.

Structure change of monoclinic ZrO2 baddeleyite involving softenings of bulk modulus and atom vibrations.

Monoclinic ZrO2 baddeleyite exhibits anomalous softenings of the bulk modulus and atom vibrations with compression. The pressure evolution of the structure is investigated using neutron powder diffraction combined with ab initio calculations. The results show that the anomalous pressure response of the bulk modulus is related not to the change in the bonding characters but to the deformation of an oxygen sublattice, especially one of the layers made of oxygen atoms in the crystallographic a* plane. The layer consists of two parallelograms; one is rotated with little distortion and the other is distorted with increasing pressure. The deformation of this layer lengthens one of the Zr-O distances, resulting in the softening of some atom vibrational modes.

Observation of Poiseuille flow of phonons in black phosphorus.

The travel of heat in insulators is commonly pictured as a flow of phonons scattered along their individual trajectory. In rare circumstances, momentum-conserving collision events dominate, and thermal transport becomes hydrodynamic. One of these cases, dubbed the Poiseuille flow of phonons, can occur in a temperature window just below the peak temperature of thermal conductivity. We report on a study of heat flow in bulk black phosphorus between 0.1 and 80 K. We find a thermal conductivity showing a faster than cubic temperature dependence between 5 and 12 K. Consequently, the effective phonon mean free path shows a nonmonotonic temperature dependence at the onset of the ballistic regime, with a size-dependent Knudsen minimum. These are hallmarks of Poiseuille flow previously observed in a handful of solids. Comparing the phonon dispersion in black phosphorus and silicon, we show that the phase space for normal scattering events in black phosphorus is much larger. Our results imply that the most important requirement for the emergence of Poiseuille flow is the facility of momentum exchange between acoustic phonon branches. Proximity to a structural transition can be beneficial for the emergence of this behavior in clean systems, even when they do not exceed silicon in purity.

Prolonged photo-carriers generated in a massive-and-anisotropic Dirac material.

Transient electron-hole pairs generated in semiconductors can exhibit unconventional excitonic condensation. Anisotropy in the carrier mass is considered as the key to elongate the life time of the pairs, and hence to stabilize the condensation. Here we employ time- and angle-resolved photoemission spectroscopy to explore the dynamics of photo-generated carriers in black phosphorus. The electronic structure above the Fermi level has been successfully observed, and a massive-and-anisotropic Dirac-type dispersions are confirmed; more importantly, we directly observe that the photo-carriers generated across the direct band gap have the life time exceeding 400 ps. Our finding confirms that black phosphorus is a suitable platform for excitonic condensations, and also open an avenue for future applications in broadband mid-infrared BP-based optoelectronic devices.

Suppression of X-ray-induced dissociation of H2O molecules in dense ice under pressure.

We investigated molecular dissociation induced by 10-keV X-ray irradiation in dense ice at pressures up to 40 GPa at 300 K. The dissociation yield estimated from the oxygen K-edge X-ray Raman spectra, showed that the molecular dissociation was enhanced up to 14 GPa and gradually suppressed on further compression to 40 GPa. The molecular dissociation was detected for a rather narrow pressure span of 2-40 GPa by the X-ray spectroscopy. The pressure variation of the dissociation yield was similar to that observed in the electric conductivity of ice VII and likely interpreted in terms of proton mobility.

O8 cluster structure of the epsilon phase of solid oxygen.

Despite many experimental and theoretical studies, the crystal structure of the epsilon phase of solid oxygen has not been determined. We performed powder x-ray diffraction experiments and the Rietveld analyses in this study to show that a new arrangement of the monoclinic space group C2/m could fit the diffraction patterns of the epsilon phase and obtained a structure that consisted of an O8 cluster with 4 molecules. The dependence of the lattice parameters, the molar volume, and the intermolecular distances on the pressure was investigated.

New helical chain structure for scandium at 240 GPa.

X-ray diffraction experiments were carried out at 297 K in order to study structural-phase transitions of the trivalent rare-earth metal scandium (Sc) at pressures of up to 297 GPa. Four stages of structural transition were observed around 23, 104, 140, and 240 GPa. The crystal structure of the highest-pressure phase, Sc-V, was found to be a hexagonal lattice (S.G.: P6(1)22 or P6(5)22) consisting of 6-screw helical chains. The lattice can be derived from modulations of the interplane stacking of the (111) planes in an fcc arrangement. The occurrence of an anisotropic structure suggests the importance of interactions between 3d orbitals with their nearest-neighbor atoms.