Emergence of superconductivity in doped H2O ice at high pressure

We investigate the possibility of achieving high-temperature superconductivity in hydrides under pressure by inducing metallization of otherwise insulating phases through doping, a path previously used to render standard semiconductors superconducting at ambient pressure. Following this idea, we study H2O, one of the most abundant and well-studied substances, we identify nitrogen as the most likely and promising substitution/dopant. We show that for realistic levels of doping of a few percent, the phase X of ice becomes superconducting with a critical temperature of about 60 K at 150 GPa. In view of the vast number of hydrides that are strongly covalent bonded, but that remain insulating up to rather large pressures, our results open a series of new possibilities in the quest for novel high-temperature superconductors

High-entropy high-hardness metal carbides discovered by entropy descriptors

High-entropy materials have attracted considerable interest due to the combination of useful properties and promising applications. Predicting their formation remains the major hindrance to the discovery of new systems. Here we propose a descriptor - entropy forming ability - for addressing synthesizability from first principles. The formalism, based on the energy distribution spectrum of randomized calculations, captures the accessibility of equally-sampled states near the ground state and quantifies configurational disorder capable of stabilizing high-entropy homogeneous phases. The methodology is applied to disordered refractory 5-metal carbides - promising candidates for high-hardness applications. The descriptor correctly predicts the ease with which compositions can be experimentally synthesized as rock-salt high-entropy homogeneous phases, validating the ansatz, and in some cases, going beyond intuition. Several of these materials exhibit hardness up to 50% higher than rule of mixtures estimations. The entropy descriptor method has the potential to accelerate the search for high-entropy systems by rationally combining first principles with experimental synthesis and characterization.Comment: 12 pages, 2 figure

Investigating the Liquid State of Carbon

Carbon materials have a many contemporary applications and new carbon allotropes are being discovered. However, while graphite and diamond are well understood, very little is known about the liquid state of carbon due to the high temperatures (above 5,000 K) and pressures (above 10 MPa) required for its formation. Initial studies used electrical heating to determine the melting point of graphite and the resistivity of liquid carbon. More recent studies used non-thermal laser melting to generate a metastable liquid that was studied with visible reflectivity and X-ray spectroscopies. Shock waves have also been used to transiently generate liquid carbon. Theoretical calculations of liquid carbon initially suggested the possibility of a liquid-liquid phase transition, but later ab initio quantum mechanical simulations showed only a continuous change in liquid coordination as its density increased. In this dissertation, extreme-UV (EUV) reflectivity and chirped coherent anti-Stokes Raman spectroscopy (c-CARS) were used to study non-thermally melted liquid carbon. Femtosecond laser pulses at 250 nm with a fluence of 0.45 J/cm2 (3.5 x 1012 W/cm2 intensity) were used to generate liquid carbon from an amorphous carbon substrate and the time evolution of EUV reflectivity was probed. EUV wavelengths from 20 to 42 nm were used with both s and p polarizations. The reflectivity decreased at all wavelengths probed as the material expanded and ablated. For wavelengths below 32 nm, the reflectivity decay time was less than ~2 ps. This time constant describes the lattice dynamics after melting, while above 32 nm, the reflectivity is also sensitive to the hot electron plasma generated by the melting pulse. From these results and equations for the behavior of a shock wave in a material, the electron temperature of the melted material was found to be 0.30 ± 0.6 eV. The reflectivity at two different polarizations was also used to calculate the complex refractive index of the material as it evolved over time. C-CARS spectra were obtained for highly ordered pyrolytic graphite (HOPG) and glassy carbon using CARS pump wavelengths of 400 nm and 800 nm. These spectra showed strong G peak resonance (1580 cm-1), corresponding to the relative vibrations of sp2 carbons in the material. The D peak (~1350 cm-1) resonance seen in Raman scattering of disordered graphite films was not observed in the CARS spectra. As this mode occurs when the excited electron scatters from a defect or phonon, it could be that the stimulated Stokes emission that occurs during the CARS process prevents such scattering. The sample was melted with an 800 nm, 90 fs laser pulse with fluences from 0.40 to 0.85 J/cm2 (intensities of 4.4 x 1012 to 9.4 x 1012 W/cm2). Delay times of less than 500 fs and as long as 100 ps all showed no broadening or shifting of the G peak, as would be expected for damaging and disordering of the material; only an intensity change is seen as the material ablates. Microscope images show permanent damage to the substrate and the fluences and times studied were comparable to those used in published reflectivity studies of liquid carbon. To advance the study of liquid carbon, a soft X-ray second harmonic generation (SHG) technique was developed and explored. X-ray absorption provides element-specific information on the electronic structure of a material that is sensitive to the environment around the element. Combining this with the interface specificity of SHG, provides a useful technique for studying solid-solid interfaces that are difficult to study otherwise. Our first soft X-ray SHG experiments on graphite films showed that the technique was indeed highly interface specific. The technique was also sensitive to resonance amplification when the input photons were at or above the carbon K-edge. A second experiment compared the boron/vacuum interface to a buried boron/carbon (Parylene-N) interface. The technique was sensitive to interface effects, showing larger SHG intensity at the boron K-edge for the boron/Parylene-N interface compared to the boron/vacuum interface. Ab initio quantum simulations were used to calculate the soft X-ray SHG spectra of these systems, verifying the interface sensitivity of the technique

Emergence of superconductivity in doped H₂O ice at high pressure

We investigate the possibility of achieving high-temperature superconductivity in hydrides under pressure by inducing metallization of otherwise insulating phases through doping, a path previously used to render standard semiconductors superconducting at ambient pressure. Following this idea, we study H2O, one of the most abundant and well-studied substances, we identify nitrogen as the most likely and promising substitution/dopant. We show that for realistic levels of doping of a few percent, the phase X of ice becomes superconducting with a critical temperature of about 60 K at 150 GPa. In view of the vast number of hydrides that are strongly covalent bonded, but that remain insulating up to rather large pressures, our results open a series of new possibilities in the quest for novel high-temperature superconductors

Effects of hydrostaticity on the structural stability of carbonates at lower mantle pressures the case study of dolomite

We have conducted high pressure far-infrared absorbance and Raman spectroscopic investigations on a natural iron-free dolomite sample up to 40 GPa. Comparison between the present observations and literature results unraveled the effect of hydrostatic conditions on the high pressure dolomite polymorph adopted close to 40 GPa, i.e. the triclinic Dol-IIIc modification. In particular, non-hydrostatic conditions impose structural disorder at these pressures, whereas hydrostatic conditions allow the detection of an ordered Dol-IIIc vibrational response. Hence, hydrostatic conditions appear to be a key ingredient for modeling carbon subduction at lower mantle conditions. Our complementary first-principles calculations verified the far-infrared vibrational response of the ambient- and high pressure dolomite phases.This study was partly supported by a Grant from Deutsche Forschungsgemeinschaft (DFG) within the Research Unit FOR2125 CarboPaT under Grants KO1260/16 and JA1469/9

Advantages and developments of Raman spectroscopy for electroceramics

Despite being applied with success in many fields of materials science, Raman spectroscopy is not yet determinant in the study of electroceramics. Recent experimental and theoretical developments, however, should increase the popularity of Raman spectroscopy in this class of materials. In this Review, we outline the fields of application of Raman spectroscopy and microscopy in various electroceramic systems, defining current key bottlenecks and explaining promising recent developments. We focus our attention to recent experimental developments, including coupling Raman spectroscopy with other methodologies, and modelling approaches involving both the model-based data interpretation and the ab initio calculation of realistic Raman spectra