Sylvain Petitgirard

• PhD in Earth Science
• Oberassistent at ETH Zurich

The densification mechanisms of silicate melts under high pressure are of key interest in understanding the evolution of the early Earth and its present‐day internal structure. Here, we report Brillouin spectroscopy‐derived transverse acoustic wave velocities VS $\left({V}_{S}\right)$ from a basaltic glass at high pressures up to 163 GPa and ambien...

The structure of mineral glasses at high pressure is often used as a model to understand corresponding melts. In this regard, silica, a prototypical oxide glass, has been studied extensively by theoretical simulations and experiments. A recent study of the oxygen K-edge x-ray Raman scattering (XRS) spectra of SiO2 glass suggested a relationship bet...

Retraction of ‘Carbon content drives high temperature superconductivity in a carbonaceous sulfur hydride below 100 GPa’ by G. Alexander Smith et al. , Chem. Commun. , 2022, 58 , 9064–9067, https://doi.org/10.1039/D2CC03170A.

Controlling the formation and stoichiometric content of desired phases of materials has become a central interest for the study of a variety of fields, notably high temperature superconductivity under extreme pressures. The further possibility of accessing metastable states by initiating reactions by x-ray triggered mechanisms over ultra-short time...

A von Hámos spectrometer has been implemented in the vacuum interaction chamber 1 of the High Energy Density instrument at the European X-ray Free-Electron Laser facility. This setup is dedicated, but not necessarily limited, to X-ray spectroscopy measurements of samples exposed to static compression using a diamond anvil cell. Si and Ge analyser c...

Much of Earth’s carbon may have been stripped away from the silicate mantle by dense metallic-iron during core formation. However, at deep magma ocean conditions carbon becomes less siderophile and thus large amounts of it may be stranded instead in the deep mantle. Here, we describe the structure and compaction mechanisms of carbonate glass to dee...

Sodium chloride is expected to be found on many of the surfaces of icy moons like Europa and Ganymede. However, spectral identification remains elusive as the known NaCl-bearing phases cannot match current observations, which require higher number of water of hydration. Working at relevant conditions for icy worlds, we report the characterization o...

The hard X-ray Kβ″ emission line shows sensitivity with respect to a wide range of cation-ligand coordination, which we investigate in the cases of GeO2 and TiO2 on the basis of ab initio spectral calculations on amorphous and crystalline structures. In compressed amorphous GeO2, the sampling of a large number of instantaneous coordination polyhedr...

A compact spectrometer for medium-resolution resonant and non-resonant X-ray emission spectroscopy in von Hámos geometry is described. The main motivation for the design and construction of the spectrometer is to allow for acquisition of non-resonant X-ray emission spectra while measuring non-resonant X-ray Raman scattering spectra at beamline ID20...

The determination of the spin state of iron-bearing compounds at high pressure and temperature is crucial for our understanding of chemical and physical properties of the deep Earth. Studies on the relationship between the coordination of iron and its electronic spin structure in iron-bearing oxides, silicates, carbonates, iron alloys, and other mi...

We report a previously unobserved superconducting state of the photosynthesized carbonaceous sulfur hydride (C-S-H) system with a maximum TC of 191(1) K below 100 GPa. The properties of C-S-H are dependent on carbon content, and X-ray diffraction and simulations reveal the system remains molecular-like up to 100 GPa.

High pressure and high temperature experiments performed with laser-heated diamond anvil cells (LH-DAC) are being extensively used in geosciences to study matter at conditions prevailing in planetary interiors. Due to the size of the apparatus itself, the samples that are produced are extremely small, on the order of few tens of micrometers. There...

The study of quartz and other silica systems under pressure is one of the most prolific domains of research over the past 50 years because of their applications in material science and fundamental relevance to planetary interiors. The characterization of the amorphous state is essential for the comprehension of pressure-induced amorphization of min...

Structure and properties of terrestrial magma oceans control the co-evolution of the core, mantle and atmosphere of the early Earth, but are poorly understood because discrepancies remain between experiments and theoretical calculations. Here we combine acoustic velocity measurements and ab initio simulations on pyrolite glass/melt with a silicate...

Carbon is an essential element for the existence and evolution of life on Earth. Its abundance in Earth's crust and mantle (the Bulk Silicate Earth, BSE) is surprisingly high given that carbon is strongly siderophile (metal-loving) at low pressures and temperatures, and hence should have segregated almost completely into Earth's core during accreti...

Carbon is an essential element for the existence and evolution of life on Earth. Its abundance in Earth's crust and mantle (the Bulk Silicate Earth, BSE) is surprisingly high given that carbon is strongly siderophile (metal-loving) at low pressures and temperatures, and hence should have segregated almost completely into Earth's core during accreti...

Room-temperature superconductivity was recently discovered in carbonaceous sulfur hydride (C-S-H) close to 3\,Mbar. We report significant differences in the superconducting response of C-S-H, with a maximum $T_{C}$ of 191(1)\,K, below a 1\,Mbar. Variations in intensity of the C-H Raman modes reveal carbon content can vary between crystals synthesiz...

The ability to tailor a material's electronic properties using density driven disordering has emerged as a powerful route to materials design. The observation of anomalous structural and electronic behavior in the rutile to CaCl2 phase transition in SnO2 led to the prediction that such behavior is inherent to all oxides experiencing such a phase tr...

Plain Language Summary Seismic studies have revealed patches on the Earth's core‐mantle boundary (CMB), which have extremely low seismic velocities. However, the origin of these so‐called ultralow‐velocity zones (ULVZs) remains unclear. One plausible source could be FeSi, which is assumed to form from chemical reactions between material from the co...

We describe the use of a silver-coated 90∘ parabolic mirror of 33 mm focal length as objective for imaging, on-axis laser heating and radiospectrometric temperature measurements of a sample compressed in a diamond anvil cell in a laser heating system. There, spatial resolution and imaging quality of the parabolic mirror are similar to the one of a...

Much of Earth’s carbon is thought to have been stripped away from the silicate mantle by dense metallic-iron to form the core ¹ . However, recent studies 2,3 suggest that a considerable part of it could have remained stranded in the deep mantle due to a change in its affinity to dissolve into iron metal-alloys at the extreme pressures and temperatu...

Significance Iron-bearing bridgmanite is the most abundant mineral in the Earth’s interior. We overcome the experimental challenge of measuring iron-bearing materials by using Brillouin scattering techniques optimized for extreme pressure conditions in combination of diamond-anvil cell. By using such techniques, results of acoustic wave velocities...

Cycling the α↔ε transformation in polycrystalline Fe is investigated using in situ x-ray diffraction under quasihydrostatic conditions. The forward α→ε transformation starts at 14±1 GPa and completes at 18±1 GPa while the reverse ε→α transformation starts at 10.5±0.5 GPa and completes at 6±1 GPa. The anomalous evolution of c/a ratios of ε-Fe measur...

A portable IR fiber laser-heating system, optimized for X-ray emission spectroscopy (XES) and nuclear inelastic scattering (NIS) spectroscopy with signal collection through the radial opening of diamond anvil cells near 90°with respect to the incident X-ray beam, is presented. The system offers double-sided on-axis heating by a single laser source...

Gibbs energy representations for ices II, III, V, and VI are reported. These were constructed using new measurements of volumes at high pressure over a range of low temperatures combined with calculated vibrational energies grounded in statistical physics. The collection of representations are released within the open source SeaFreeze program, toge...

Recent studies have revealed that Earth's deep mantle may have a wider range of oxygen fugacities than previously thought. Such a large heterogeneity might be caused by material subducted into the deep mantle. However, high‐pressure phase relations are poorly known in systems including Fe³⁺ at the top of the lower mantle, where the subducted slab m...

Germanium oxide is a prototype network-forming oxide with pressure-induced structural changes similar to those found in crystals and amorphous silicate oxides at high pressure. Studying density and coordination changes in amorphous GeO2 allows for insight into structural changes in silicate oxides at very high pressure, with implications for the pr...

We present a new diamond anvil cell design, hereafter called mBX110, that combines both the advantages of a membrane and screws to generate high pressure. It enables studies at large-scale facilities for many synchrotron X-ray techniques and has the possibility to remotely control the pressure with the membrane as well as the use of the screws in t...

Gibbs energy representations for ice III, V and VI are reported. These were constructed using new measurements of volumes at high pressure over a range of low temperatures combined with calculated vibrational energies grounded in statistical physics. The collection of representations including ice Ih and water (released as the open source SeaFreeze...

Knowledge of the behavior of hydrogen in metal hydrides is the key for understanding their electronic properties. Here, we present an 1 H-NMR study of cubic FeH up to 202 GPa. We observe a distinct deviation from the ideal metallic behavior between 64 and 110 GPa that suggests pressure-induced H-H interactions. Accompanying ab initio calculations s...

Understanding the dynamics of the magmatic evolution of the interior of the Moon requires accurate knowledge of the viscosity (η) of lunar magmas at high pressure (P) and high temperature (T) conditions. Although the viscosities of terrestrial magmas are relatively well-documented, and their relation to magma composition well-studied, the viscositi...

Significance Diamond is a uniquely attractive wide-bandgap semiconductor for future electronic devices where its remarkable physical properties may enable switches, transistors, and diodes for extreme applications. Whereas p-type semiconducting diamond is well developed with boron doping, the synthesis of n-type diamond, required to complete purely...

Studies of the behaviour of solids at ultra-high pressures, those beyond 200 GPa, contribute to our fundamental understanding of materials properties and allow an insight into the processes happening at such extreme conditions relevant for terrestrial and extra-terrestrial bodies. The behaviour of magnesium oxide, MgO, is of a particular importance...

Three experiments are reviewed, performed (in 2014–2016) at ID18 of ESRF to measure the influence of acceleration on time dilation by measuring the relative shift between the absorption lines of two states of the same rotating absorber with accelerations anti-parallel and parallel to the incident beam. Statistically significant data for rotation fr...

Knowledge of the behavior of hydrogen in metal hydrides is the key for understanding their electronic properties. So far, no experimental methods exist to access these properties beyond 100 GPa, where high-Tc superconductivity emerges. Here, we present an 1H-NMR study of cubic FeH up to 200GPa. We observe a distinct deviation from the ideal metalli...

SiO2 is the main component of silicate melts and thus controls their network structure and physical properties. The compressibility and viscosities of melts at depth are governed by their short range atomic and electronic structure. We measured the O K-edge and the Si L2,3-edge in silica up to 110 GPa using X-ray Raman scattering spectroscopy, and...

We measure valence-to-core x-ray emission spectra of compressed crystalline GeO2 up to 56 GPa and of amorphous GeO2 up to 100 GPa. In a novel approach, we extract the Ge coordination number and mean Ge-O distances from the emission energy and the intensity of the Kβ′′ emission line. The spectra of high-pressure polymorphs are calculated using the B...

Metal-silicate partitioning studies performed in high pressure, laser-heated diamond anvil cells (DAC) are commonly used to explore element distribution during planetary-scale core-mantle differentiation. The small run-products contain suitable areas for analysis commonly less than tens of microns in diameter and a few microns thick. Because high s...

X-ray emission and x-ray Raman scattering spectroscopy are powerful tools to investigate the local electronic and atomic structure of high and low Z elements in-situ. Notably, these methods can be applied for in-situ spectroscopy at high pressure and high temperature using resistively or laser-heated diamond anvil cells in order to achieve thermody...

The pyrite mineral MnS2 was recently shown to undergo a giant pressure-induced volume collapse at ∼ 12 GPa, via a disordered intermediate phase. The high pressure arsenopyrite phase is stabilised by metal-metal bonding, a mechanism now shown to be ubiquitous for Mn²⁺ chalcogenides. Here we report a spectroscopic investigation of this transition up...

Hydrogen bond symmetrisations in H-bonded systems triggered by pressure-induced nuclear quantum effects (NQEs) is a long-known concept but experimental evidence in high-pressure ices has remained elusive with conventional methods. Theoretical works predicted quantum-mechanical tunneling of protons within water ices to occur at pressures above 30 GP...

Natural specimens of the pyrochlore (A2B2O7) compounds have been found to retain foreign actinide impurities within their parent framework, undergoing metamictization to a fully amorphous state. The response to radionuclide decay identifies pyrochlore systems with having high radiation tolerance and tailored use in radioactive waste applications an...

The aim of the experiment series was to test the influence of acceleration on time dilation by measuring the relative spectral shift between the resonance spectra of a rotating Mossbauer absorber with acceleration anti-parallel and parallel to the direction of the incident beam. Based on the experiences and know-how acquired in our previous experim...

Hydrogen bond symmetrisations in H-bonded systems triggered by pressure induced nuclear quantum effects (NQEs) is a long-known concept1 but experimental evidences in high-pressure ices have remained elusive with conventional methods2,3. Theoretical works predicted quantum-mechanical tunneling of protons within water ices to occur at pressures above...

The past 15 years have seen an astonishing increase in Nuclear Magnetic Resonance (NMR) sensitivity and accessible pressure range in high-pressure NMR experiments, owing to a series of new developments of NMR spectroscopy applied to the diamond anvil cell (DAC). Recently, with the application of electro-magnetic lenses, so-called Lenz lenses, in to...

A new pathway to nuclear magnetic resonance (NMR) spectroscopy for picoliter-sized samples (including those kept in harsh and extreme environments, particularly in diamond anvil cells) is introduced, using inductively coupled broadband passive electromagnetic lenses, to locally amplify the magnetic field at the isolated sample, leading to an increa...

The convection or settling of matter in the deep Earth’s interior is mostly constrained by density variations between the different reservoirs. Knowledge of the density contrast between solid and molten silicates is thus of prime importance to understand and model the dynamic behavior of the past and present Earth. SiO2 is the main constituent of E...

The presence of carbonates in inclusions in diamonds coming from depths exceeding 670 km are obvious evidence that carbonates exist in the Earth’s lower mantle. However, their range of stability, crystal structures and the thermodynamic conditions of the decarbonation processes remain poorly constrained. Here we investigate the behaviour of pure ir...

The rheology of eclogite, garnetite and clinopyroxenite in the peridotitic upper mantle was experimentally investigated in a large volume press combined with in situ synchrotron X-ray diffraction techniques to study the impact on mantle convection resulting from the subduction of oceanic lithosphere. Experiments were carried out over a range of con...

A new pathway to nuclear magnetic resonance spectroscopy in high pressure diamond anvil cells is introduced, using inductively coupled broadband passive electro-magnetic lenses to locally amplify the magnetic flux at the isolated sample, leading to an increase in sensitivity. The lenses are adopted for the geometrical restrictions imposed by a toro...

Water-rich planetary bodies including large icy moons and ocean exoplanets may host a deep liquid water ocean underlying a high-pressure icy mantle. The latter is often considered as a limitation to the habitability of the uppermost ocean because it would limit the availability of nutrients resulting from the hydrothermal alteration of the silicate...

Density and structural changes of matter in their liquid or amorphous form, such as silicates melts, molecular fluids, or glasses, are of extreme importance to model the interior of planetary bodies. However, measuring the evolution of amorphous materials under extreme conditions of pressure and temperature remains challenging mainly because of the...

X-ray Raman scattering (XRS) spectroscopy is an inelastic scattering method that uses hard X-rays of the order of 10 keV to measure energy-loss spectra at absorption edges of light elements (Si, Mg, O etc.), with an energy resolution below 1 eV. The high-energy X-rays employed with this technique can penetrate thick or dense sample containers such...

A method to separate the non-resonant inelastic X-ray scattering signal of a micro-metric sample contained inside a diamond anvil cell (DAC) from the signal originating from the high-pressure sample environment is described. Especially for high-pressure experiments, the parasitic signal originating from the diamond anvils, the gasket and/or the pre...

The high-pressure behaviour of ammonium metal formates has been investigated using high-pressure single-crystal X-ray diffraction on ammonium iron and nickel formates, and neutron powder diffraction on ammonium zinc formate in the pressure range of 0-2.3 GPa. A structural phase transition in the pressure range of 0.4-1.4 GPa, depending on the metal...

The incorporation of noble gas atoms, in particular neon, into the pores of network structures is very challenging due to the weak interactions they experience with the network solid. Using high-pressure single-crystal X-ray diffraction, we demonstrate that neon atoms enter into the extended network of ammonium metal formates, thus forming compound...

Materials combining the hardness and strength of diamond with the higher thermal stability of cubic boron nitride (cBN) have broad potential value in science and engineering. Reacting nanodiamond with cBN at moderate pressures and high temperatures provides a pathway to such materials. Here we report the fabrication of Cx-BN nanocomposites, measuri...

Studies of materials’ properties at high and ultrahigh pressures lead to discoveries of unique physical and chemical phenomena and a deeper understanding of matter. In high-pressure research, an achievable static pressure limit is imposed by the strength of available strong materials and design of high-pressure devices. Using a high-pressure and hi...

Significance A new technique has been developed to measure in situ the density of amorphous material composed of light elements under extreme conditions of pressure using the X-ray absorption method. At core–mantle boundary (CMB) pressure, the densities of MgSiO 3 glass and melts are similar to the one of the crystalline bridgmanite, within uncerta...

Developments in pulsed laser heating applied to nuclear resonance techniques are presented together with their applications to studies of geophysically relevant materials. Continuous laser heating in diamond anvil cells is a widely used method to generate extreme temperatures at static high pressure conditions in order to study the structure and pr...

We simulated the redox decomposition of magnesium-siderite at pressures and temperatures corresponding to the top of the Earth's D″ layer (135 GPa and 2650 K). It transforms into new phases, with unexpected stoichiometry. We report their crystal structure, based on single-crystal synchrotron radiation diffraction on a multi-grain sample, using a ch...

A detailed description is presented of the Extreme Conditions Beamline P02.2 for micro X-ray diffraction studies of matter at simultaneous high pressure and high/low temperatures at PETRA III, in Hamburg, Germany. This includes performance of the X-ray optics and instrumental resolution as well as an overview of the different sample environments av...