Phase diagram of Na x CoO 2 ͑x տ 0.71͒ has been reinvestigated using electrochemically fine-tuned single crystals. Both phase-separation and staging phenomena as a result of sodium multivacancy cluster ordering have been found. Phase-separation phenomenon is observed in the narrow ranges of 0.76Շ x Շ 0.82 and 0.83Շ x Շ 0.86. While x = 0.820 shows A-type antiferromagnetic ͑A-AF͒ ordering below 22 K, x = 0.833 is confirmed to have a magnetic ground state of A-AF ordering below ϳ8 K and is only reachable through slow cooling. In addition, x = 0.859 is found to be responsible for the highest A-AF transition temperature at about 29 K. Staging model based on ordered stacking of multivacancy layers is proposed to explain the hysteretic behavior and A-AF correlation length for x ϳ0.82-0.86.
We studied the defects of Bi2Se3 generated from Bridgman growth of stoichiometric and nonstoichiometric self-fluxes. Growth habit, lattice size, and transport properties are strongly affected by the types of defect generated. Major defect types of BiSe antisite and partial Bi2-layer intercalation are identified through combined studies of direct atomic-scale imaging with scanning transmission electron microscopy (STEM) in conjunction with energy-dispersive X-ray spectroscopy (STEM-EDX), X-ray diffraction, and Hall effect measurements. We propose a consistent explanation to the origin of defect type, growth morphology, and transport property.
Electronic phase diagram of LixCoO2 has been re-examined using potentiostatically deintercalated single crystal samples. Stable phases of x ∼ 0.87, 0.72, 0.53, 0.50, 0.43, and 0.33 were found and isolated for physical property studies. A-type and chain-type antiferromagnetic orderings have been suggested from magnetic susceptibility measurement results in x ∼ 0.87 and 0.50 below ∼ 10K and 200K, respectively, similar to those found in NaxCoO2 system. There is no Li vacancy superlattice ordering observed at room temperature for the electronically stable phase Li0.72CoO2 as revealed by synchrotron X-ray Laue diffraction. The peculiar magnetic anomaly near ∼175K as often found in powder samples of x∼0.46-0.78 cannot be isolated through this single crystal potentiostatic method, which supports the previously proposed explanation to be surface stabilized phase of significant thermal hysteresis and aging character.
The three dimensional (3D) Dirac semimetal is a new quantum state of matter that has attracted much attention recently in physics and material science. Here, we report on the growth of large plate-like single crystals of Cd3As2 in two major orientations by a self-selecting vapor growth (SSVG) method, and the optimum growth conditions have been experimentally determined. The crystalline imperfections and electrical properties of the crystals were examined with transmission electron microscopy (TEM), scanning tunneling microscopy (STM), and transport property measurements. This SSVG method makes it possible to control the as-grown crystal compositions with excess Cd or As leading to mobilities near 5–105 cm2V−1s−1. Zn-doping can effectively reduce the carrier density to reach the maximum residual resistivity ratio (RRRρ300K/ρ5K) of 7.6. A vacuum-cleaved single crystal has been investigated using angle-resolved photoemission spectroscopy (ARPES) to reveal a single Dirac cone near the center of the surface Brillouin zone with a binding energy of approximately 200 meV.
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