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Pressure induced evolution of band structure in black phosphorus studied by $^{31}$P-NMR

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 Added by Takuto Fujii
 Publication date 2019
  fields Physics
and research's language is English




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Two-dimensional layered semiconductor black phosphorus (BP), a promising pressure induced Dirac system as predicted by band structure calculations, has been studied by $^{31}$P-nuclear magnetic resonance. Band calculations have been also carried out to estimate the density of states $D(E)$. The temperature and pressure dependences of nuclear spin lattice relaxation rate $1/T_1$ in the semiconducting phase are well reproduced using the derived $D(E)$, and the resultant pressure dependence of semiconducting gap is in good accordance with previous reports, giving a good confirmation that the band calculation on BP is fairly reliable. The present analysis of $1/T_1$ data with the complemental theoretical calculations allows us to extract essential information, such as the pressure dependences of $D(E)$ and chemical potential, as well as to decompose observed $1/T_1$ into intrinsic and extrinsic contributions. An abrupt increase in $1/T_1$ at 1.63GPa indicates that the semiconducting gap closes, resulting in an enhancement of conductivity.



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162 - Z. J. Xiang , G. J. Ye , C. Shang 2015
In a semimetal, both electron and hole carriers contribute to the density of states at the Fermi level. The small band overlaps and multi-band effects give rise to many novel electronic properties, such as relativistic Dirac fermions with linear dispersion, titanic magnetoresistance and unconventional superconductivity. Black phosphorus has recently emerged as an exceptional semiconductor with high carrier mobility and a direct, tunable bandgap. Of particular importance is the search for exotic electronic states in black phosphorus, which may amplify the materials potential beyond semiconductor devices. Here we show that a moderate hydrostatic pressure effectively suppresses the band gap and induces a Lifshitz transition from semiconductor to semimetal in black phosphorus; a colossal magnetoresistance is observed in the semimetallic phase. Quantum oscillations in high magnetic field reveal the complex Fermi surface topology of the semimetallic black phosphorus. In particular, a Dirac-like fermion emerges at around 1.2 GPa, which is continuously tuned by external pressure. The observed semi-metallic behavior greatly enriches black phosphoruss material property, and sets the stage for the exploration of novel electronic states in this material. Moreover, these interesting behaviors make phosphorene a good candidate for the realization of a new two-dimensional relativistic electron system, other than graphene.
We present a detailed $^{31}$P nuclear magnetic resonance (NMR) study of the molecular rotation in the compound [Cu(pz)$_{2}$(2-HOpy)$_{2}$](PF$_{6}$)$_{2}$, where pz = C$_4$H$_4$N$_2$ and 2-HOpy = C$_5$H$_4$NHO. Here, a freezing of the PF$_6$ rotation modes is revealed by several steplike increases of the temperature-dependent second spectral moment, with accompanying broad peaks of the longitudinal and transverse nuclear spin-relaxation rates. An analysis based on the Bloembergen-Purcell-Pound (BPP) theory quantifies the related activation energies as $E_{a}/k_{B}$ = 250 and 1400 K. Further, the anisotropy of the second spectral moment of the $^{31}$P absorption line was calculated for the rigid lattice, as well as in the presence of several sets of PF$_6$ reorientation modes, and is in excellent agreement with the experimental data. Whereas the anisotropy of the frequency shift and enhancement of nuclear spin-relaxation rates is driven by the molecular rotation with respect to the dipole fields stemming from the Cu ions, the second spectral moment is determined by the intramolecular interaction of nuclear $^{19}$F and $^{31}$P moments in the presence of the distinct rotation modes.
The phase diagrams of correlated systems like cuprates or pnictides high-temperature superconductors are characterized by a topological change of the Fermi surface under continuous variation of an external parameter, the so-called Lifshitz transition. However, the large number of low-temperature instabilities and the interplay of multiple energy scales complicate the study of this phenomenon. Here we first identify the optical signatures of a pressure-induced Lifshitz transition in a clean elemental system, black phosphorus. By applying external pressures above 1.5 GPa, we observe a change in the pressure dependence of the Drude plasma frequency due to the appearance of massless Dirac fermions. At higher pressures, optical signatures of two structural phase transitions are also identified. Our findings suggest that a key fingerprint of the Lifshitz transition in solid state systems, and in absence of structural phase transitions, is a discontinuity of the Drude plasma frequency due to the change of Fermi surface topology.
241 - C. Q. Han , M. Y. Yao , X. X. Bai 2014
Electronic structures of single crystalline black phosphorus were studied by state-of-art angleresolved photoemission spectroscopy. Through high resolution photon energy dependence measurements, the band dispersions along out-of-plane and in-plane directions are experimentally determined. The electrons were found to be more localized in the ab-plane than that is predicted in calculations. Beside the kz-dispersive bulk bands, resonant surface state is also observed in the momentum space. Our finds strongly suggest that more details need to be considered to fully understand the electronic properties of black phosphorus theoretically.
We performed $^{31}$P-NMR measurements on LaFe(As$_{1-x}$P$_{x}$)O to investigate the relationship between antiferromagnetism and superconductivity. The antiferromagnetic (AFM) ordering temperature $T_{rm N}$ and the moment $mu_{rm ord}$ are continuously suppressed with increasing P content $x$ and disappear at $x = 0.3$ where bulk superconductivity appears. At this superconducting $x = 0.3$, quantum critical AFM fluctuations are observed, indicative of the intimate relationship between superconductivity and low-energy AFM fluctuations associated with the quantum-critical point in LaFe(As$_{1-x}$P$_{x}$)O. The relationship is similar to those observed in other isovalent-substitution systems, e.g., BaFe$_{2}$(As$_{1-x}$P$_{x}$)$_{2}$ and SrFe$_{2}$(As$_{1-x}$P$_{x}$)$_{2}$, with the 122 structure. Moreover, the AFM order reappears with further P substitution ($x > 0.4$). The variation of the ground state with respect to the P substitution is considered to be linked to the change in the band character of Fe-3$d$ orbitals around the Fermi level.
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