Lead selenide, PbSe, an important lead chalcogenide semiconductor, has been investigated using in-situ high-pressure/high-temperature synchrotron X-ray diffraction and electrical resistivity measurements. For the first time, high-quality X-ray diffraction data were collected for the intermediate orthorhombic PbSe. Combined with ab initio calculations, we find a Cmcm, InI-type symmetry for the intermediate phase, which is structurally more favorable than the anti-GeS-type Pnma. At room temperature, the onset of the cubic-orthorhombic transition was observed at ∼3.5 GPa with a ∼3.4% volume reduction. At an elevated temperature of 1000 K, the reversed orthorhombic-to-cubic transition was observed at 6.12 GPa, indicating a positive Clapeyron slope for the phase boundary. Interestingly, phase-transition induced elastic softening in PbSe was also observed, which can be mainly attributed to the loosely bonded trigonal prisms along the b-axis in the Cmcm structure. In a comparison with the cubic phase, orthorhombic PbSe exhibits a large negative pressure dependence of electrical resistivity. In addition, thermoelastic properties of orthorhombic PbSe have been derived from isothermal compression data, such as the temperature derivative of bulk modulus and thermally induced pressure.

The stability, structure and properties of carbonate minerals at lower mantle conditions has significant impact on our understanding of the global carbon cycle and the composition of the interior of the Earth. In recent years, there has been significant interest in the behavior of carbonates at lower mantle conditions, specifically in their carbon hybridization, which has relevance for the storage of carbon within the deep mantle. Using high-pressure synchrotron X-ray diffraction in a diamond anvil cell coupled with direct laser heating of CaCO3 using a CO2 laser, we identify a crystalline phase of the material above 40 GPa − corresponding to a lower mantle depth of around 1,000 km − which has first been predicted by ab initio structure predictions. The observed sp 2 carbon hybridized species at 40 GPa is monoclinic with P 21/c symmetry and is stable up to 50 GPa, above which it transforms into a structure which cannot be indexed by existing known phases. A combination of ab initio random structure search (AIRSS) and quasi-harmonic approximation (QHA) calculations are used to re-explore the relative phase stabilities of the rich phase diagram of CaCO3. Nudged elastic band (NEB) calculations are used to investigate the reaction mechanisms between relevant crystal phases of CaCO3 and we postulate that the mineral is capable of undergoing sp 2 -sp 3 hybridization change purely in the P 21/c structure − forgoing the accepted post-aragonite P mmn structure.

The application of pressure allows systematic tuning of the charge density of a material cleanly, that is, without changes to the chemical composition via dopants, and exploratory high‐pressure experiments can inform the design of bulk syntheses of materials that benefit from their properties under compression. The electronic and structural response of semiconducting tin nitride Sn3N4 under compression is now reported. A continuous opening of the optical band gap was observed from 1.3 eV to 3.0 eV over a range of 100 GPa, a 540 nm blue‐shift spanning the entire visible spectrum. The pressure‐mediated band gap opening is general to this material across numerous high‐density polymorphs, implicating the predominant ionic bonding in the material as the cause. The rate of decompression to ambient conditions permits access to recoverable metastable states with varying band gaps energies, opening the possibility of pressure‐tuneable electronic properties for future applications.

We present a CO laser heating setup for synchrotron x-ray diffraction inside a diamond anvil cell, situated at HPCAT (Sector 16, Advanced Photon Source, Argonne National Lab, Illinois, USA), which is modular and portable between the HPCAT experiment hutches. The system allows direct laser heating of wide bandgap insulating materials to thousands of degrees at static high pressures up to the Mbar regime. Alignment of the focused CO laser spot is performed using a mid-infrared microscope, which addressed past difficulties with aligning the invisible radiation. The implementation of the mid-infrared microscope alongside a mirror pinhole spatial filter system allows precise alignment of the heating laser spot and optical pyrometry measurement location to the x-ray probe. A comparatively large heating spot (∼50 m) relative to the x-ray beam (<10 m) reduces the risk of temperature gradients across the probed area. Each component of the heating system and its diagnostics have been designed with portability in mind and compatibility with the various experimental hutches at the HPCAT beamlines. We present measurements on ZrO at 5.5 GPa which demonstrate the improved room-temperature diffraction data quality afforded by annealing with the CO laser. We also present measurements at 5.5 GPa up to 2800 K in which we do not observe the postulated fluorite ZrO structure, in agreement with recent findings.

The application of pressure allows systematic tuning of the charge density of a material cleanly, that is, without changes to the chemical composition via dopants, and exploratory high‐pressure experiments can inform the design of bulk syntheses of materials that benefit from their properties under compression. The electronic and structural response of semiconducting tin nitride Sn3N4 under compression is now reported. A continuous opening of the optical band gap was observed from 1.3 eV to 3.0 eV over a range of 100 GPa, a 540 nm blue‐shift spanning the entire visible spectrum. The pressure‐mediated band gap opening is general to this material across numerous high‐density polymorphs, implicating the predominant ionic bonding in the material as the cause. The rate of decompression to ambient conditions permits access to recoverable metastable states with varying band gaps energies, opening the possibility of pressure‐tuneable electronic properties for future applications.