Zhenhai Yu

Structural phase transitions in Bi2Se3 under high pressure

Raman spectroscopy and angle dispersive X-ray diffraction (XRD) experiments of bismuth selenide (Bi2Se3) have been carried out to pressures of 35.6 and 81.2 GPa, respectively, to explore its pressure-induced phase transformation. The experiments indicate that a progressive structural evolution occurs from an ambient rhombohedra phase (Space group (SG): R-3m) to monoclinic phase (SG: C2/m) and eventually to a high pressure body-centered tetragonal phase (SG: I4/mmm). Evidenced by our XRD data up to 81.2 GPa, the Bi2Se3 crystallizes into body-centered tetragonal structures rather than the recently reported disordered body-centered cubic (BCC) phase. Furthermore, first principles theoretical calculations favor the viewpoint that the I4/mmm phase Bi2Se3 can be stabilized under high pressure (>30 GPa). Remarkably, the Raman spectra of Bi2Se3 from this work (two independent runs) are still Raman active up to ~35 GPa. It is worthy to note that the disordered BCC phase at 27.8 GPa is not observed here. The remarkable difference in atomic radii of Bi and Se in Bi2Se3 may explain why Bi2Se3 shows different structural behavior than isocompounds Bi2Te3 and Sb2Te3.

Conventional empirical law reverses in the phase transitions of 122-type iron-based superconductors

Phase transition of solid-state materials is a fundamental research topic in condensed matter physics, materials science and geophysics. It has been well accepted and widely proven that isostructural compounds containing different cations undergo same pressure-induced phase transitions but at progressively lower pressures as the cation radii increases. However, we discovered that this conventional law reverses in the structural transitions in 122-type iron-based superconductors. In this report, a combined low temperature and high pressure X-ray diffraction (XRD) measurement has identified the phase transition curves among the tetragonal (T), orthorhombic (O) and the collapsed-tetragonal (cT) phases in the structural phase diagram of the iron-based superconductor AFe2As2 (A = Ca, Sr, Eu, and Ba). The cation radii dependence of the phase transition pressure (T → cT) shows an opposite trend in which the compounds with larger ambient radii cations have a higher transition pressure.

Pressure-Induced Crystallization and Phase Transformation of Para-xylene.

Static pressure is an alternative method to chemical pressure for tuning the crystal structure, bonds, and physical properties of materials, and is a significant technique for the synthesis of novel materials and fundamental research. In this letter, we report the crystallization and phase transformation of p-xylene under high pressure. Our optical micrographic observations and the appearance of lattice modes in the Raman and infrared (IR) spectra indicated that p-xylene crystallizes at ∼0.1 GPa. The X-ray diffraction (XRD) pattern at 0.84 GPa suggests that the crystallized p-xylene had a monoclinic phase with the Cc(9) space group. The sharp shrinkage of the lattice at ~13 GPa and the solid state of the decompressed sample we observed suggests a new crystalline phase of p-xylene. The in situ XRD showed that the new crystalline phase was still a monoclinic structure but with a different space group of C2(5), indicating that a phase transition occurred during further compression. The mass spectrometry experiment confirmed phase transition polymerization, with mainly trimer and tetramer polymers. Our findings suggest an easy and efficient method for crystallizing and polymerizing p-xylene under high pressure.

Correlated structural and electronic phase transformations in transition metal chalcogenide under high pressure

Here, we report comprehensive studies on the high-pressure structural and electrical transport properties of the layered transition metal chalcogenide (Cr2S3) up to 36.3 GPa. A structural phase transition was observed in the rhombohedral Cr2S3 near 16.5 GPa by the synchrotron angle dispersive X-ray diffraction measurement using a diamond anvil cell. Through in situ resistance measurement, the electric resistance value was detected to decrease by an order of three over the pressure range of 7–15 GPa coincided with the structural phase transition. Measurements on the temperature dependence of resistivity indicate that it is a semiconductor-to-metal transition in nature. The results were also confirmed by the electronic energy band calculations. Above results may shed a light on optimizing the performance of Cr2S3 based applications under extreme conditions.

Anomalous anisotropic compression behavior of superconducting CrAs under high pressure

Significance We preformed high-pressure structural studies of CrAs to understand the physical mechanism of its pressure-induced superconductivity. It was found that the lattice parameters a and c both demonstrate a nonmonotonic change, and the lattice parameter b undergoes a rapid contraction at ∼0.18–0.35 GPa, which suggests that a pressure-induced isostructural phase transition occurs in CrAs. Above the phase transition pressure, the axial compressibilities of CrAs present remarkable anisotropy. The pressure-related structural changes occurred concurrently with the appearance of bulk superconductivity, shedding light on the structural and related electronic responses to high pressure, which play a key role toward understanding the superconductivity of CrAs. CrAs was observed to possess the bulk superconductivity under high-pressure conditions. To understand the superconducting mechanism and explore the correlation between the structure and superconductivity, the high-pressure structural evolution of CrAs was investigated using the angle-dispersive X-ray diffraction (XRD) method. The structure of CrAs remains stable up to 1.8 GPa, whereas the lattice parameters exhibit anomalous compression behaviors. With increasing pressure, the lattice parameters a and c both demonstrate a nonmonotonic change, and the lattice parameter b undergoes a rapid contraction at ∼0.18−0.35 GPa, which suggests that a pressure-induced isostructural phase transition occurs in CrAs. Above the phase transition pressure, the axial compressibilities of CrAs present remarkable anisotropy. A schematic band model was used to address the anomalous compression behavior of CrAs. The present results shed light on the structural and related electronic responses to high pressure, which play a key role toward understanding the superconductivity of CrAs.

Structural evolution behavior of manganese monophosphide under high pressure: experimental and theoretical study

The influence of external pressure on the structural properties of manganese monophosphides (MnP) at room temperature has been studied using in situ angle dispersive synchrotron x-ray powder diffraction (AD-XRD) with a diamond anvil cell. The crystal structure of MnP is stable between 0 to 15 GPa. However, the compressibility of b-axis is much larger than those of a- and c-axes. From this result we suggested that the occurrence of superconductivity in MnP was induced by suppression of the long-range antiferromagnetically ordered state rather than a structural phase transition. Furthermore, the present experimental results show that the Pnma phase of MnP undergoes a pressure-induced structural phase transition at ~15.0 GPa. This finding lighted up-to-date understanding of the common prototype B31 structure (Strukturbericht Designation: B31) in transition metal monophosphides. No additional structural phase transition was observed up to 35.1 GPa (Run 1) and 40.2 GPa (Run 2) from the present AD-XRD results. With an extensive crystal structure searching and ab initio calculations, we predict that MnP underwent two pressure-induced structural phase transitions of Pnma  →  P213 and P213  →  Pm-3m (CsCl-type) at 55.0 and 92.0 GPa, respectively. The structural stability and the electronic structures of manganese monophosphides under high pressure are also briefly discussed.

Pressure-induced phase transitions of exposed curved surface nano-TiO2 with high photocatalytic activity

We report a unique phase transition in compressed exposed curved surface nano-TiO2 with high photocatalytic activity using in situ synchrotron X-ray diffraction and Raman Spectroscopy. High-pressure studies indicate that the anatase phase starts to transform into baddeleyite phase upon compression at 19.4 GPa, and completely transforms into the baddeleyite phase above 24.6 GPa. Upon decompression, the baddeleyite phase was maintained until the pressure was released to 6.4 GPa and then transformed into the α-PbO2 phase at 2.7 GPa. Together with the results of high-resolution transmission electron microscopy and the pressure-volume relationship, this phase transitions characteristics during the compression-decompression cycle demonstrate that the truncated biconic morphology possessed excellent stability. This study may provide an insight to the mechanisms of stability for high photocatalytic activity of nano-TiO2.

Author Correction: Pressure-Induced Crystallization and Phase Transformation of Para-xylene

A correction to this article has been published and is linked from the HTML and PDF versions of this paper. The error has not been fixed in the paper.

Unexpected Semimetallic BiS2 at High Pressure and High Temperature

In the past decade, the group V-VI compounds have been widely investigated due to their excellent properties and applications. It is now accepted that diverse stoichiometry can yield new compounds with unanticipated properties, uncovering potentially new physicochemical mechanisms. However, in this group, aside from the conventional A2B3-type, no other energetically stable stoichiometry has been reported yet. Here, we report that Bi2S3 is unstable and decomposes into stoichiometric BiS2 and BiS with different Bi valence states upon compression. Encouragingly, we successfully synthesized the predicted BiS2 phase and thus, confirmed its existence. Our current calculations reveal that the found BiS2 phase is a semimetal, associated with the increased concentration of nonmetallic S. The present results represent the first counterintuitive stable stoichiometry of group V-VI and provide a good example in designing and synthesizing new compounds under compression.

Size-dependent phase transition of Er2O3 under high pressure

The size effect on the structural and optical properties of cubic Er2O3 was investigated under pressure by in-situ angular dispersive synchrotron x-ray diffraction (AD-XRD), Raman scattering, photo...