Laser-heated Diamond Anvil Cell Research Articles

Synthesis and Characterization of Lithium Pyrocarbonate (Li2[C2O5]) and Lithium Hydrogen Pyrocarbonate (Li[HC2O5]).

The anhydrous pyrocarbonate and the first hydrogen pyrocarbonate Li[HC2O5] have been synthesized in a laser-heated diamond anvil cell at moderate pressures ( GPa). The structures of the two compounds have been obtained from single crystal X-ray diffraction data. Raman spectroscopy and DFT calculations have been employed to further characterize their structure-property relations. The present results significantly enlarge the group of inorganic pyrocarbonates by the discovery of the hydrogenated pyrocarbonate anion Li[HC2O5]-. In the structure of Li[HC2O5] there is a symmetric O-H-O arrangement at high pressures, which converts to a conventional O-H O hydrogen bond upon pressure release.

High pressure and high temperature synthesis of a new boron carbide phase

The dense boron carbide (B-C) phases with diamond structure are predicted to be superhard, with hardness close to that of a cubic boron nitride (c-BN). At ambient conditions, graphite-like BC3 is well characterized, firstly reported by Kouvetakis et al. In this work, we have synthesized a new B-C phase from the graphite-like BC3 in a laser-heated diamond anvil cell. Interestingly, this phase could be recoverable to ambient pressure due to dynamic stabilities. The Raman spectrum and X-ray diffraction patterns give the possible structure of this new phase.

High-pressure synthesis of rhenium carbide Re3C under megabar compression

The rhenium carbide Re3C was predicted to be stable under high pressure and expected to have high hardness and low compressibility. In this study, we realise the synthesis of Re3C at megabar pressures of 105(3) and 140(5) GPa in laser-heated diamond anvil cells and characterise its structure using synchrotron single-crystal X-ray diffraction. The structure of Re3C has the monoclinic space group C2/m and is built of CRe7 capped octahedra. Our combined ab initio calculations and quantitative topological analysis support experimental structural data and further deepen the understanding of the chemical bonding in the newly synthesized compound.

Inversion of the temperature dependence of thermal conductivity of hcp iron under high pressure

Investigating how the thermal transport properties of iron change under extremely high pressure and temperature conditions, such as those found in the Earth’s core, is a major experimental challenge. Over the past decade, there has been a great deal of discussion and debate surrounding the thermal conductivity of the iron-based Earth’s core and its thermal evolution. One reason for this may be the variability in the experimentally obtained thermal conductivity of iron at high pressures and temperatures. In this study, we present the experimental results of measuring the thermal conductivity of hexagonal-closed-pack (hcp) iron over a wide pressure-temperature range up to 176 GPa and 2900 K using the pulsed light heating thermoreflectance technique in a laser-heated diamond anvil cell. Our findings indicate that the temperature derivative of the thermal conductivity of hcp iron undergoes a change from negative to positive above 74 GPa, potentially making hcp iron highly conductive at conditions similar to those observed in the Earth’s core. This observation represents a notable example of a phenomenon where pressure appears to influence the sign of the temperature derivative of the thermal conductivity of an isostructural metal.

6-Fold-Coordinated Beryllium in Calcite-Type Be[CO3

The anhydrous beryllium carbonate Be[CO3] with calcite-type crystal structure was obtained by a reaction of BeO with CO2 in a laser-heated diamond anvil cell at pressures between 30 GPa and 80 GPa and elevated temperatures. Its calcite-type crystal structure (R3̅c with Z = 6) is characterized by 6-fold-coordinated beryllium atoms forming [BeO6] octahedra and by trigonal-planar [CO3]2- groups. The crystal structure was determined by synchrotron-based single-crystal X-ray diffraction and confirmed by density-functional-theory-based calculations in combination with experimental Raman spectroscopy. Calcite-type Be[CO3] was synthesized at significantly lower pressures than the other very few compounds hosting 6-fold-coordinated beryllium, and it is the first beryllium carbonate with this coordination.

Polytypism of incommensurately modulated structures of crystalline bromine upon molecular dissociation under high pressure

Polytypism of incommensurately modulated structures was hitherto unobserved. Here, it was found in solid bromine and iodine upon molecular dissociation under pressure up to 112 GPa. Single-crystal synchrotron x-ray diffraction in laser-heated diamond anvil cells revealed a number of allotropes of bromine and iodine, including polytypes of Br-IIIγ (Fmmm(00γ)s00) with γ varying within 0.18 to 0.3, coexisting at a given pressure. This finding opens a research area in the field of solid-solid phase transitions, disordered states of solid matter, and high-pressure structural studies. Published by the American Physical Society 2024

Synthesis and crystal structure of acentric anhydrous beryllium carbonate Be(CO3).

The anhydrous alkaline earth metal carbonate Be(CO3) was synthesized in a laser-heated diamond anvil cell at moderate pressures and temperatures (20(2) GPa and 1500(200) K) by a reaction of BeO with CO2. It crystallizes in the acentric, trigonal space group P3121 with Z = 3. The crystal structure was obtained from synchrotron single crystal X-ray diffraction data and confirmed by density functional theory-based calculations in combination with Raman spectroscopy. Second harmonic generation measurements were employed to verify the acentric space group symmetry. The crystal structure of Be(CO3) is characterized by the presence of isolated [CO3]2--groups and BeO4-tetrahedra. This is a new structure type and such a topology has not been observed in carbonates before. Be(CO3) can be recovered to ambient conditions and is not undergoing a phase transition during decompression.

Phase diagram of ruthenium characterized In Situ by synchrotron X-ray diffraction and Ab Initio simulations

In this work, an in situ characterization of the high-pressure and high-temperature phase diagram of ruthenium was carried out. This experiment was performed using a combination of laser-heated diamond anvil cell (LH-DAC) and X-ray diffraction (XRD) techniques at the beamline ID27 of the European Synchrotron Radiation Facility (ESRF). XRD patterns were collected in the range of 15 GPa to 110 GPa and from ambient temperature up to 6600 K. While the hcp-fcc transition, predicted to occur at elevated temperatures was not observed, this study has produced the first experimental observation of a solid–liquid phase transition of Ru at HP conditions. A P-V-T equation of state valid up to 100 GPa and 3000 K is reported.

Exotic compounds of monovalent calcium synthesized at high pressure

It is well known that atoms of the same element in different valence states show very different chemical behaviors. Calcium is a typical divalent metal, sharing or losing both of its valence electrons when forming compounds. Attempts have been made to synthesize compounds of monovalent calcium ions for decades, but with very little success (e.g., in clusters). Pressure can result in substantial changes in the properties of atoms and chemical bonding, creating an extensive variety of unique materials with special valence states. In this study, using the ab initio evolutionary algorithm USPEX, we search for stable calcium–chlorine (Ca–Cl) system compounds at pressures up to 100 GPa. Besides the expected compound CaCl2, we predict three new compounds with monovalent Ca to be stable at high pressures, namely, CaCl, Ca5Cl6, and Ca3Cl4. According to our calculations, CaCl is stable at pressures above 18 GPa and is predicted to undergo a transition from nonmagnetic Fm-3m-CaCl to ferromagnetic Pm-3m-CaCl at 40 GPa. Ca5Cl6 and Ca3Cl4 are stable at pressures above 37 and 73 GPa, with space groups P-1 and R-3, respectively. Following these predictions, we successfully synthesized Pm-3m-CaCl in laser-heated diamond anvil cell experiments. The emergence of the unusual valence state at high pressures reveals exciting opportunities for creating entirely new materials in sufficiently large quantities for a variety of potential applications.

All-Single Bonds Fused N18 Macro-Rings and N8 Cagelike Building Blocks Stabilized in Lanthanum Supernitrides.

Single-bonded polymeric nitrogen has gained tremendous research interest because of its unique physical properties and great potential applications. Despite much progress in theoretical predictions, it is still challenging to experimentally synthesize polynitrogen compounds with novel all-single-bonded units. Herein, we have synthesized two brand-new lanthanum supernitrides LaN8, through a direct reaction between La and N2 in laser-heated diamond anvil cells at megabar pressures. Our experiments and calculations revealed that two LaN8 phases had the R-3 and P4/n symmetry characterized by a unique 2D network with N18 macro-rings and cagelike N8 building blocks, respectively. Differing from known polynitrogen structures, these two polymers were composed of single-bonded nitrogen atoms belonging to sp3 and sp2 hybridizations. In particular, P4/n LaN8 possessed the longest N-N bond length among all of the experimentally reported metal nitrides, potentially being a high-energy-density material. The present study opens a fresh, promising avenue for the rational design and discovery of new supernitrides with unique nitrogen structures via the high-pressure treatment.

Improving the creation of SiV centers in diamond via sub-μs pulsed annealing treatment

Silicon-vacancy (SiV) centers in diamond are emerging as promising quantum emitters in applications such as quantum communication and quantum information processing. Here, we demonstrate a sub-μs pulsed annealing treatment that dramatically increases the photoluminescence of SiV centers in diamond. Using a silane-functionalized adamantane precursor and a laser-heated diamond anvil cell, the temperature and energy conditions required to form SiV centers in diamond were mapped out via an optical thermometry system with an accuracy of ±50 K and a 1 μs temporal resolution. Annealing scheme studies reveal that pulsed annealing can obviously minimize the migration of SiV centers out of the diamond lattice, and a 2.5-fold increase in the number of emitting centers was achieved using a series of 200-ns pulses at a 50 kHz repetition rate via acousto-optic modulation. Our study provides a novel pulsed annealing treatment approach to improve the efficiency of the creation of SiV centers in diamond.

Hydrogenation of calcite and change in chemical bonding at high pressure: Diamond formation above 100 GPa

Synchrotron X-ray diffraction (XRD) and Raman spectroscopy in laser heated diamond anvil cells and first principles molecular dynamics (FPMD) calculations have been used to investigate the reactivity of calcite and molecular hydrogen (H2) at high pressures up to 120 GPa. We find that hydrogen reacts with calcite starting below 0.5 GPa at room temperature forming chemical bonds with carbon and oxygen. This results in the unit cell volume expansion; the hydrogenation level is much higher for powdered samples. Single-crystal XRD measurements at 8–24 GPa reveal the presence of previously reported III, IIIb, and VI calcite phases; some crystallites show up to 4% expansion, which is consistent with the incorporation of ≤ 1 hydrogen atom per formula unit. At 40–102 GPa XRD patterns of hydrogenated calcite demonstrate broadened features consistent with the calcite VI structure with incorporated hydrogen atoms. Above 80 GPa, the CO stretching mode of calcite splits suggesting a change in the coordination of CO bonds. Laser heating at 110 GPa results in the formation of CC bonds manifested in the crystallization of diamond recorded by in situ XRD at 300 K and 110 GPa and by Raman spectroscopy on recovered samples commenced with C13 calcite. We explored several theoretical models, which show that incorporation of atomic hydrogen results in local distortions of CO3 groups, formation of corner-shared CO polyhedra, and chemical bonding of H to C and O, which leads to the lattice expansion and vibrational features consistent with the experiments. The experimental and theoretical results support recent reports on tetrahedral C coordination in high-pressure carbonate glasses and suggest a possible source of the origin of ultradeep diamonds.

High-Pressure oC16-YBr3 Polymorph Recoverable to Ambient Conditions: From 3D Framework to Layered Material.

Exfoliation of graphite and the discovery of the unique properties of graphene─graphite's single layer─have raised significant attention to layered compounds as potential precursors to 2D materials with applications in optoelectronics, spintronics, sensors, and solar cells. In this work, a new orthorhombic polymorph of yttrium bromide, oC16-YBr3 was synthesized from yttrium and CBr4 in a laser-heated diamond anvil cell at 45 GPa and 3000 K. The structure of oC16-YBr3 was solved and refined using in situ synchrotron single-crystal X-ray diffraction. At high pressure, it can be described as a 3D framework of YBr9 polyhedra, but upon decompression below 15 GPa, the structure motif changes to layered, with layers comprising edge-sharing YBr8 polyhedra weakly bonded by van der Waals interactions. The layered oC16-YBr3 material can be recovered to ambient conditions, and according to Perdew-Burke-Ernzerhof-density functional theory calculations, it exhibits semiconductor properties with a band gap that is highly sensitive to pressure. This polymorph possesses a low exfoliation energy of 0.30 J/m2. Our results expand the list of layered trivalent rare-earth metal halides and provide insights into how high pressure alters their structural motifs and physical properties.

Melting experiments on Fe-S-O-C alloys at Martian core conditions: Possible structures in the O- and C-bearing core of Mars

Recent seismological studies of the Martian core revealed its relatively low density, suggesting the presence of large amounts of light elements including oxygen and carbon in addition to sulfur. In order to reveal crystallizing solids in the light-element-rich core of Mars, we performed high-pressure melting experiments on Fe-S-O-C alloys at 26–49 GPa using a laser-heated diamond-anvil cell. The liquidus phase relations in the Fe-S-O-C system were determined based on textural and chemical characterizations of recovered samples. The results show that Fe-S-O-C liquids crystallize FeO or Fe3C in the presence of small amounts of O or C in liquids. Accordingly the liquidus fields of Fe3S and Fe2S are small, and the quaternary eutectic point is found to be close to the Fe-Fe3S binary eutectic point. Under Martian core conditions, S-rich liquids have low liquidus temperatures to crystallize FeO or Fe3C compared to S-poor liquids. The pressure dependence of liquidus temperatures suggests that crystallization of Mars’ core starts at the center upon cooling. According to the FeO-Fe3C cotectic surfaces and their liquidus temperatures, an FeO and/or Fe3C inner core is predicted unless the Martian core remains entirely liquid.

High-pressure dysprosium carbides containing carbon dimers, trimers, chains, and ribbons

Exploring the chemistry of materials at high pressure leads to discoveries of previously unknown compounds and phenomena. Here chemical reactions between elemental dysprosium and carbon were studied in laser-heated diamond anvil cells at pressures up to 95 GPa and temperatures of ∼2800 K. In situ single-crystal synchrotron X-ray diffraction (SCXRD) analysis of the reaction products revealed the formation of novel dysprosium carbides, γ-DyC2, Dy5C9, and γ-Dy4C5, along with previously reported Dy3C2 and Dy4C3. The crystal structures of γ-DyC2 and Dy5C9 feature infinite flat carbon polyacene-like ribbons and cis-polyacetylene-type chains, respectively. In the structure of γ-Dy4C5, carbon atoms form dimers and non-linear trimers. Dy3C2 contains ethanide-type carbon dumbbells, and Dy4C3 is methanide featuring single carbon atoms. Density functional theory calculations reproduce well the crystal structures of high-pressure dysprosium carbides and reveal conjugated π-electron systems in novel infinite carbon polyanions. This work demonstrates that complex carbon homoatomic species previously unknown in organic chemistry can be synthesized at high pressures by direct reactions of carbon with metals.

High-Pressure Synthesis of the Iodide Carbonate Na5(CO3)2I

Here, we present the synthesis of a novel quaternary compound, iodide carbonate Na5(CO3)2I, at 18(1) and 25.1(5) GPa in laser-heated diamond anvil cells. Single-crystal synchrotron X-ray diffraction provides accurate structural data for Na5(CO3)2I and shows that the structure of the material can be described as built of INa8 square prisms, distorted NaO6 octahedra, and trigonal planar CO32− units. Decompression experiments show that the novel iodide carbonate is recoverable in the N2 atmosphere to ambient conditions. Our ab initio calculations agree well with the experimental structural data, provide the equation of state, and shed light on the chemical bonding and electronic properties of the new compound.

Structural Phase Transition and Decomposition of XeF2 under High Pressure and Its Formation of Xe-Xe Covalent Bonds.

Noble gases with inert chemical properties have rich bonding modes under high pressure. Interestingly, Xe and Xe form covalent bonds, originating from the theoretical simulation of the pressure-induced decomposition of XeF2, which has yet to be experimentally confirmed. Moreover, the structural phase transition and metallization of XeF2 under high pressure have always been controversial. Therefore, we conducted extensive experiments using a laser-heated diamond anvil cell technique to investigate the above issues of XeF2. We propose that XeF2 undergoes a structural phase transition and decomposition above 84.1 GPa after laser heating, and the decomposed product Xe2F contains Xe-Xe covalent bonds. Neither the pressure nor temperature alone could bring about these changes in XeF2. With our UV-vis absorption experiment, I4/mmm-XeF2 was metalized at 159 GPa. This work confirms the existence of Xe-Xe covalent bonds and provides insights into the controversy surrounding XeF2, enriching the research on noble gas chemistry under high pressure.

In Situ Measurement Techniques Using Diamond Anvil Cell at High Pressure–Temperature Conditions: A Review

Diamond anvil cells have garnered significant attention in high‐pressure studies as a valuable tool for investigating material preparation, phase transition dynamics, and ultra‐high‐pressure physical chemistry. Its potential applications span fields such as materials science, condensed matter physics, chemistry, and geology. This study conducts a comprehensive review of the utilization of laser‐heated diamond anvil cell (LH‐DAC) devices in conjunction with in situ optical characterization techniques, such as X‐Ray and Raman scattering. Further, diverse in situ performance measurement methods encompassing electrical, thermal, magnetic, and acoustic analyses are examined. The development and role of the prevailing in situ measurement techniques have been described, along with the current progress in applied research for each technique. This study aims to facilitate the discovery of new structures and properties of materials under high pressure–temperature conditions.

Pressure stabilizes ferrous iron in bridgmanite under hydrous deep lower mantle conditions

Earth’s lower mantle is a potential water reservoir. The physical and chemical properties of the region are in part controlled by the Fe3+/ΣFe ratio and total iron content in bridgmanite. However, the water effect on the chemistry of bridgmanite remains unclear. We carry out laser-heated diamond anvil cell experiments under hydrous conditions and observe dominant Fe2+ in bridgmanite (Mg, Fe)SiO3 above 105 GPa under the normal geotherm conditions corresponding to depth > 2300 km, whereas Fe3+-rich bridgmanite is obtained at lower pressures. We further observe FeO in coexistence with hydrous NiAs-type SiO2 under similar conditions, indicating that the stability of ferrous iron is a combined result of H2O effect and high pressure. The stability of ferrous iron in bridgmanite under hydrous conditions would provide an explanation for the nature of the low-shear-velocity anomalies in the deep lower mantle. In addition, entrainment from a hydrous dense layer may influence mantle plume dynamics and contribute to variations in the redox conditions of the mantle.

Nitrogen sequestration in the core at megabar pressure and implications for terrestrial accretion

Nitrogen (N) is the most abundant element in Earth’s atmosphere, but is extremely depleted in the silicate Earth. However, it is not clear whether core sequestration or early atmospheric loss was responsible for this depletion. Here we study the effect of core formation on the inventory of nitrogen using laser-heated diamond anvil cells. We find that, due to the simultaneous dissolution of oxygen in the metal, N becomes much less siderophile (iron-loving) at pressures and temperatures up to 104 GPa and 5000 K, a thermodynamic condition relevant to the bottom of the magma ocean in the aftermath of the moon-forming giant impact. Using a core–mantle–atmosphere coevolution model, we show that the impact-induced processes (core formation and/or atmospheric loss) are unlikely to account for the observed N anomaly, which is instead best explained by the accretion of mainly N-poor impactors. The terrestrial volatile pattern requires severe N depletion on precursor bodies, prior to their accretion to the proto-Earth.