Magnetism in cold subducting slabs at mantle transition zone depths.

The Earth's crust-mantle boundary, the Mohorovicic discontinuity, has been traditionally considered to be the interface between the magnetic crust and the non-magnetic mantle1. However, this assumption has been questioned by geophysical observations2,3 and by the identification of magnetic remanence in mantle xenoliths4, which suggest mantle magnetic sources. Owing to their high critical temperatures, iron oxides are the only potential sources of magnetic anomalies at mantle depths5. Haematite (α-Fe2O3) is the dominant iron oxide in subducted lithologies at depths of 300 to 600 kilometres, delineated by the thermal decomposition of magnetite and the crystallization of a high-pressure magnetite phase deeper than about 600 kilometres6. The lack of data on the magnetic properties of haematite at relevant pressure-temperature conditions, however, hinders the identification of magnetic boundaries within the mantle and their contribution to observed magnetic anomalies. Here we apply synchrotron Mössbauer source spectroscopy in laser-heated diamond anvil cells to investigate the magnetic transitions and critical temperatures in Fe2O3 polymorphs7 at pressures and temperatures of up to 90 gigapascals and 1,300 kelvin, respectively. Our results show that haematite remains magnetic at the depth of the transition zone in the Earth's mantle in cold or very cold subduction geotherms, forming a frame of deep magnetized rocks in the West Pacific region. The deep magnetic sources spatially correlate with preferred paths of the Earth's virtual geomagnetic poles during reversals8 that might not reflect the geometry of the transitional field. Rather, the paths might be an artefact caused by magnetized haematite-bearing rocks in cold subducting slabs at mid-transition zone depths. Such deep sources should be taken into account when carrying out inversions of the Earth's geomagnetic data9, and especially in studies of planetary bodies that no longer have a dynamo10, such as Mars.

Sub-micrometer focusing setup for high-pressure crystallography at the Extreme Conditions beamline at PETRA†III.

Scientific tasks aimed at decoding and characterizing complex systems and processes at high pressures set new challenges for modern X-ray diffraction instrumentation in terms of X-ray flux, focal spot size and sample positioning. Presented here are new developments at the Extreme Conditions beamline (P02.2, PETRA III, DESY, Germany) that enable considerable improvements in data collection at very high pressures and small scattering volumes. In particular, the focusing of the X-ray beam to the sub-micrometer level is described, and control of the aberrations of the focusing compound refractive lenses is made possible with the implementation of a correcting phase plate. This device provides a significant enhancement of the signal-to-noise ratio by conditioning the beam shape profile at the focal spot. A new sample alignment system with a small sphere of confusion enables single-crystal data collection from grains of micrometer to sub-micrometer dimensions subjected to pressures as high as 200 GPa. The combination of the technical development of the optical path and the sample alignment system contributes to research and gives benefits on various levels, including rapid and accurate diffraction mapping of samples with sub-micrometer resolution at multimegabar pressures.

Revealing the Complex Nature of Bonding in the Binary High-Pressure Compound FeO_{2}.

Extreme pressures and temperatures are known to drastically affect the chemistry of iron oxides, resulting in numerous compounds forming homologous series nFeOmFe_{2}O_{3} and the appearance of FeO_{2}. Here, based on the results of in situ single-crystal x-ray diffraction, Mössbauer spectroscopy, x-ray absorption spectroscopy, and density-functional theory+dynamical mean-field theory calculations, we demonstrate that iron in high-pressure cubic FeO_{2} and isostructural FeO_{2}H_{0.5} is ferric (Fe^{3+}), and oxygen has a formal valence less than 2. Reduction of oxygen valence from 2, common for oxides, down to 1.5 can be explained by a formation of a localized hole at oxygen sites.

The most incompressible metal osmium at static pressures above 750 gigapascals.

Metallic osmium (Os) is one of the most exceptional elemental materials, having, at ambient pressure, the highest known density and one of the highest cohesive energies and melting temperatures. It is also very incompressible, but its high-pressure behaviour is not well understood because it has been studied so far only at pressures below 75 gigapascals. Here we report powder X-ray diffraction measurements on Os at multi-megabar pressures using both conventional and double-stage diamond anvil cells, with accurate pressure determination ensured by first obtaining self-consistent equations of state of gold, platinum, and tungsten in static experiments up to 500 gigapascals. These measurements allow us to show that Os retains its hexagonal close-packed structure upon compression to over 770 gigapascals. But although its molar volume monotonically decreases with pressure, the unit cell parameter ratio of Os exhibits anomalies at approximately 150 gigapascals and 440 gigapascals. Dynamical mean-field theory calculations suggest that the former anomaly is a signature of the topological change of the Fermi surface for valence electrons. However, the anomaly at 440 gigapascals might be related to an electronic transition associated with pressure-induced interactions between core electrons. The ability to affect the core electrons under static high-pressure experimental conditions, even for incompressible metals such as Os, opens up opportunities to search for new states of matter under extreme compression.

Breakdown of Magnetic Order in the Pressurized Kitaev Iridate ß-Li_{2}IrO_{3}.

Temperature-pressure phase diagram of the Kitaev hyperhoneycomb iridate ß-Li_{2}IrO_{3} is explored using magnetization, thermal expansion, magnetostriction, and muon spin rotation measurements, as well as single-crystal x-ray diffraction under pressure and ab initio calculations. The Néel temperature of ß-Li_{2}IrO_{3} increases with the slope of 0.9 K/GPa upon initial compression, but the reduction in the polarization field H_{c} reflects a growing instability of the incommensurate order. At 1.4 GPa, the ordered state breaks down upon a first-order transition, giving way to a new ground state marked by the coexistence of dynamically correlated and frozen spins. This partial freezing in the absence of any conspicuous structural defects may indicate the classical nature of the resulting pressure-induced spin liquid, an observation paralleled to the increase in the nearest-neighbor off-diagonal exchange Γ under pressure.

Role of disorder in the thermodynamics and atomic dynamics of glasses.

We measured the density of vibrational states (DOS) and the specific heat of various glassy and crystalline polymorphs of SiO2. The typical (ambient) glass shows a well-known excess of specific heat relative to the typical crystal (α-quartz). This, however, holds when comparing a lower-density glass to a higher-density crystal. For glassy and crystalline polymorphs with matched densities, the DOS of the glass appears as the smoothed counterpart of the DOS of the corresponding crystal; it reveals the same number of the excess states relative to the Debye model, the same number of all states in the low-energy region, and it provides the same specific heat. This shows that glasses have higher specific heat than crystals not due to disorder, but because the typical glass has lower density than the typical crystal.

Hyperfine splitting and room-temperature ferromagnetism of Ni at multimegabar pressure.

Magnetic and elastic properties of Ni metal have been studied up to 260 GPa by nuclear forward scattering of synchrotron radiation with the 67.4 keV Mössbauer transition of 61Ni. The observed magnetic hyperfine splitting confirms the ferromagnetic state of Ni up to 260 GPa, the highest pressure where magnetism in any material has been observed so far. Ab initio calculations reveal that the pressure evolution of the hyperfine field, which features a maximum in the range of 100 to 225 GPa, is a relativistic effect. The Debye energy obtained from the Lamb-Mössbauer factor increases from 33 meV at ambient pressure to 60 meV at 100 GPa. The change of this energy over volume compression is well described by a Grüneisen parameter of 2.09.

Importance of correlation effects in hcp iron revealed by a pressure-induced electronic topological transition.

We discover that hcp phases of Fe and Fe(0.9)Ni(0.1) undergo an electronic topological transition at pressures of about 40 GPa. This topological change of the Fermi surface manifests itself through anomalous behavior of the Debye sound velocity, c/a lattice parameter ratio, and Mössbauer center shift observed in our experiments. First-principles simulations within the dynamic mean field approach demonstrate that the transition is induced by many-electron effects. It is absent in one-electron calculations and represents a clear signature of correlation effects in hcp Fe.

High-pressure reactions between the pnictogens: the rediscovery of BiN.

We explore chemical reactions within pnictogens with an example of bismuth and nitrogen under extreme conditions. Understanding chemical reactions between Bi and N, elements representing the first and the last stable elements of the nitrogen group, and the physical properties of their compounds under ambient and high pressure is far from being complete. Here, we report the high-pressure high-temperature synthesis of orthorhombic Pbcn BiN (S.G. #60) from Bi and N2 precursors at pressures above 40 GPa. Using synchrotron single-crystal X-ray diffraction on the polycrystalline sample, we solved and refined the compound's structure and studied its behavior and compressibility on decompression to ambient pressure. We confirm the stability of Pbcn BiN to pressures as low as 12.5(4) GPa. Below that pressure value, a group-subgroup phase transformation occurs, resulting in the formation of a non-centrosymmetric BiN solid with a space group Pca21 (S.G. #29). We use ab initio calculations to characterize the polymorphs of BiN. They also provide support and explanation for our experimental observations, in particular those corresponding to peculiar Bi-N bond evolution under pressure, resulting in a change in the coordination numbers of Bi and N as a function of pressure within the explored stability field of Pbcn BiN.

An insight into what superconducts in polycrystalline boron-doped diamonds based on investigations of microstructure.

The discovery of superconductivity in polycrystalline boron-doped diamond (BDD) synthesized under high pressure and high temperatures [Ekimov, et al. (2004) Nature 428:542-545] has raised a number of questions on the origin of the superconducting state. It was suggested that the heavy boron doping of diamond eventually leads to superconductivity. To justify such statements more detailed information on the microstructure of the composite materials and on the exact boron content in the diamond grains is needed. For that we used high-resolution transmission electron microscopy and electron energy loss spectroscopy. For the studied superconducting BDD samples synthesized at high pressures and high temperatures the diamond grain sizes are approximately 1-2 mum with a boron content between 0.2 (2) and 0.5 (1) at %. The grains are separated by 10- to 20-nm-thick layers and triangular-shaped pockets of predominantly (at least 95 at %) amorphous boron. These results render superconductivity caused by the heavy boron doping in diamond highly unlikely.

Isothermal equation of state of crystalline and glassy materials from optical measurements in diamond anvil cells.

Here, we present a method to study the equation of state of opaque amorphous and crystalline materials in diamond anvil cells. The approach is based on measurements of sample dimensions using high-resolution optical microscopy. Data on the volumetric strain as a function of pressure allow deriving the isothermal equation of state of the studied material. The analysis of optical images is fully automatized and allows measuring the sample dimensions with the precision of about 60 nm. The methodology was validated by studying isothermal compression of ω-Ti up to 30 GPa in a Ne pressure transmitting medium. Within the accuracy of the measurements, the bulk modulus of ω-Ti determined using optical microscopy was similar to that obtained from x-ray diffraction. For glassy carbon compressed to ∼30 GPa, the previously unknown bulk modulus was found to be equal to K0 = 28 (2) GPa [K' = 5.5(5)].

Combining FIB milling and conventional Argon ion milling techniques to prepare high-quality site-specific TEM samples for quantitative EELS analysis of oxygen in molten iron.

This paper reports a procedure to combine the focused ion beam micro-sampling method with conventional Ar-milling to prepare high-quality site-specific transmission electron microscopy cross-section samples. The advantage is to enable chemical and structural evaluations of oxygen dissolved in a molten iron sample to be made after quenching and recovery from high-pressure experiments in a laser-heated diamond anvil cell. The evaluations were performed by using electron energy-loss spectroscopy and high-resolution transmission electron microscopy. The high signal to noise ratios of electron energy-loss spectroscopy core-loss spectra from the transmission electron microscopy thin foil, re-thinned down to 40 nm in thickness by conventional Argon ion milling, provided us with oxygen quantitative analyses of the quenched molten iron phase. In addition, we could obtain lattice-fringe images using high-resolution transmission electron microscopy. The electron energy-loss spectroscopy analysis of oxygen in Fe(0.94)O has been carried out with a relative accuracy of 2%, using an analytical procedure proposed for foils thinner than 80 nm. Oxygen K-edge energy-loss near-edge structure also allows us to identify the specific phase that results from quenching and its electronic structure by the technique of fingerprinting of the spectrum with reference spectra in the Fe-O system.

Portable laser-heating system for diamond anvil cells.

The diamond anvil cell (DAC) technique coupled with laser heating has become the most successful method for studying materials in the multimegabar pressure range at high temperatures. However, so far all DAC laser-heating systems have been stationary: they are linked either to certain equipment or to a beamline. Here, a portable laser-heating system for DACs has been developed which can be moved between various analytical facilities, including transfer from in-house to a synchrotron or between synchrotron beamlines. Application of the system is demonstrated in an example of nuclear inelastic scattering measurements of ferropericlase (Mg(0.88)Fe(0.12))O and h.c.p.-Fe(0.9)Ni(0.1) alloy, and X-ray absorption near-edge spectroscopy of (Mg(0.85)Fe(0.15))SiO(3) majorite at high pressures and temperatures. Our results indicate that sound velocities of h.c.p.-Fe(0.9)Ni(0.1) at pressures up to 50 GPa and high temperatures do not follow a linear relation with density.

An ultradense polymorph of rutile with seven-coordinated titanium from the Ries crater.

We report the discovery of an ultradense post-rutile polymorph of titanium dioxide in shocked gneisses of the Ries crater in Germany. The microscopic diagnostic feature is intense blue internal reflections in crossed polarizers in reflected light. X-ray diffraction studies revealed a monoclinic lattice, isostructural with the baddeleyite ZrO2 polymorph, and the titanium cation is coordinated with seven oxygen anions. The cell parameters are as follows: a = 4.606(2) angstroms, b = 4.986(3) angstroms, c = 4.933(3) angstroms, beta (angle between c and a axes) = 99.17(6) degrees; space group P2(1)/c; density = 4.72 grams per cubic centimeter, where the numbers in parentheses are standard deviations in the last significant digits. This phase is 11% denser than rutile. The mineral is sensitive to x-ray irradiation and tends to invert to rutile. The presence of baddeleyite-type TiO2 in the shocked rocks indicates that the peak shock pressure was between 16 and 20 gigapascals, and the post-shock temperature was much lower than 500 degrees C.

Synchrotron X-ray Study of Iron at High Pressure and Temperature.

X-ray synchrotron experiments with in situ laser heating of iron in a diamond-anvil cell show that the high-pressure epsilon phase, a hexagonal close-packed (hcp) structure, transforms to another phase (possibly a polytype double-layer hcp) at a pressure of about 38 gigapascals and at temperatures between 1200 and 1500 kelvin. This information has implications for the phase relations of iron in Earth's core.

Structural stability of the sigma phase FeCr under pressure up to 77 GPa.

A tetragonal σ phase of the equiatomic FeCr alloy was investigated by x-ray diffraction under pressure up to 77 GPa. The phase was found to be stable in the whole pressure range studied. The equation of state for the tetragonal phase was found to have a value of bulk modulus K(0) = 217(5) GPa and its pressure derivative was K(0)' = 5.8(2), which makes it less compressible than the constituent elements. Electronic factors governing the σ phase stability are discussed in relation to the Hume-Rothery mechanism.

Pressure-induced phase transitions of AX(2)-type iron pnictides: an ab initio study.

An investigation into the high-pressure behavior of AX(2)-type iron pnictides was conducted using first-principles calculations based on density functional theory within the generalized gradient approximation. Our results demonstrate that a phase transition from the marcasite to the CuAl(2) occurs at 108 GPa for FeP(2), at 92 GPa for FeAs(2), and at 38 GPa for FeSb(2), accompanying a semiconductor-to-metal crossover. A linear relationship between bulk moduli and the inverse specific volume is proposed to be B(0) = 17 498/V(0)-45.9 GPa for the marcasite-type phase and B(0) = 31 798/V(0)-67.5 GPa for the CuAl(2)-type phase. According to the observed structural evolutions, we claim that the regular marcasite transforms to the CuAl(2)-type phase and the anomalous marcasite transforms to the pyrite-type phase at high pressures.

Magnetic and electronic properties of magnetite across the high pressure anomaly.

The magnetite Fe3O4, being anciently known magnetic material to human kind and remaining in leading positions for development of advanced technologies presently, demonstrates a number of puzzling physical phenomena, being at focus of extensive research for more than century. Recently the pressure-induced anomalous behavior of physical properties of magnetite in vicinity of the structural phase transition, occurring at P ~ 25-30 GPa, has attracted particular attention, and its nature remains unclear. Here we study the magnetic and electronic properties of magnetite across high pressure anomaly and in the pressure-induced phase by means of 57Fe synchrotron Moessbauer spectroscopy and neutron diffraction. The hyperfine interaction parameters behavior was systematically analysed over pressure 0-40 GPa and temperature 10-290 K ranges. In the high pressure phase the ferrimagnetic order formation below TNP ~ 420 K was observed and spin arrangement symmetry was deduced. The structural, magnetic and electronic phase diagram of magnetite in the discussed pressure range is established.

Fe-N system at high pressure reveals a compound featuring polymeric nitrogen chains.

Poly-nitrogen compounds have been considered as potential high energy density materials for a long time due to the large number of energetic N-N or N=N bonds. In most cases high nitrogen content and stability at ambient conditions are mutually exclusive, thereby making the synthesis of such materials challenging. One way to stabilize such compounds is the application of high pressure. Here, through a direct reaction between Fe and N2 in a laser-heated diamond anvil cell, we synthesize three ironnitrogen compounds Fe3N2, FeN2 and FeN4. Their crystal structures are revealed by single-crystal synchrotron X-ray diffraction. Fe3N2, synthesized at 50 GPa, is isostructural to chromium carbide Cr3C2. FeN2 has a marcasite structure type and features covalently bonded dinitrogen units in its crystal structure. FeN4, synthesized at 106 GPa, features polymeric nitrogen chains of [N42-]n units. Based on results of structural studies and theoretical analysis, [N42-]n units in this compound reveal catena-poly[tetraz-1-ene-1,4-diyl] anions.

Metastable silica high pressure polymorphs as structural proxies of deep Earth silicate melts.

Modelling of processes involving deep Earth liquids requires information on their structures and compression mechanisms. However, knowledge of the local structures of silicates and silica (SiO2) melts at deep mantle conditions and of their densification mechanisms is still limited. Here we report the synthesis and characterization of metastable high-pressure silica phases, coesite-IV and coesite-V, using in situ single-crystal X-ray diffraction and ab initio simulations. Their crystal structures are drastically different from any previously considered models, but explain well features of pair-distribution functions of highly densified silica glass and molten basalt at high pressure. Built of four, five-, and six-coordinated silicon, coesite-IV and coesite-V contain SiO6 octahedra, which, at odds with 3rd Pauling's rule, are connected through common faces. Our results suggest that possible silicate liquids in Earth's lower mantle may have complex structures making them more compressible than previously supposed.