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High pressure induces dramatic changes and novel phenomena in condensed volatiles1,2 that are usually not preserved after recovery from pressure vessels. Here we report a process that pressurizes volatiles into nanopores of type 1 glassy carbon precursors, converts glassy carbon into nanocrystalline diamond by heating and synthesizes free-standing nanostructured diamond capsules (NDCs) capable of permanently preserving volatiles at high pressures, even after release back to ambient conditions for various vacuum-based diagnostic probes including electron microscopy. As a demonstration, we perform a comprehensive study of a high-pressure argon sample preserved in NDCs. Synchrotron X-ray diffraction and high-resolution transmission electron microscopy show nanometre-sized argon crystals at around 22.0 gigapascals embedded in nanocrystalline diamond, energy-dispersive Xray spectroscopy provides quantitative compositional analysis and electron energy-loss spectroscopy details the chemical bonding nature of high-pressure argon. The preserved pressure of the argon sample inside NDCs can be tuned by controlling NDC synthesis pressure. To test the general applicability of the NDC process, we show that high-pressure neon can also be trapped in NDCs and that type 2 glassy carbon can be used as the precursor container material. Further experiments on other volatiles and carbon allotropes open the possibility of bringing high-pressure explorations on a par with mainstream condensed-matter investigations and applications.
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The distribution, accumulation and circulation of oxygen and hydrogen in Earth's interior dictate the geochemical evolution of the hydrosphere, atmosphere and biosphere. The oxygen-rich atmosphere and iron-rich core represent two end-members of the oxygen-iron (O-Fe) system, overlapping with the entire pressure-temperature-composition range of the planet. The extreme pressure and temperature conditions of the deep interior alter the oxidation states, spin states and phase stabilities of iron oxides, creating new stoichiometries, such as Fe4O5 (ref. 5) and Fe5O6 (ref. 6). Such interactions between O and Fe dictate Earth's formation, the separation of the core and mantle, and the evolution of the atmosphere. Iron, in its multiple oxidation states, controls the oxygen fugacity and oxygen budget, with hydrogen having a key role in the reaction of Fe and O (causing iron to rust in humid air). Here we use first-principles calculations and experiments to identify a highly stable, pyrite-structured iron oxide (FeO2) at 76 gigapascals and 1,800 kelvin that holds an excessive amount of oxygen. We show that the mineral goethite, FeOOH, which exists ubiquitously as 'rust' and is concentrated in bog iron ore, decomposes under the deep lower-mantle conditions to form FeO2 and release H2. The reaction could cause accumulation of the heavy FeO2-bearing patches in the deep lower mantle, upward migration of hydrogen, and separation of the oxygen and hydrogen cycles. This process provides an alternative interpretation for the origin of seismic and geochemical anomalies in the deep lower mantle, as well as a sporadic O2 source for the Great Oxidation Event over two billion years ago that created the present oxygen-rich atmosphere.
Asunto(s)
Atmósfera/química , Planeta Tierra , Compuestos Férricos/química , Hidrógeno/química , Compuestos de Hierro/química , Minerales/química , Oxígeno/química , Ecosistema , Historia Antigua , Hierro/química , Oxidación-Reducción , Oxígeno/análisis , Presión , Sulfuros/química , TemperaturaRESUMEN
The cycling of hydrogen influences the structure, composition, and stratification of Earth's interior. Our recent discovery of pyrite-structured iron peroxide (designated as the P phase) and the formation of the P phase from dehydrogenation of goethite FeO2H implies the separation of the oxygen and hydrogen cycles in the deep lower mantle beneath 1,800 km. Here we further characterize the residual hydrogen, x, in the P-phase FeO2Hx Using a combination of theoretical simulations and high-pressure-temperature experiments, we calibrated the x dependence of molar volume of the P phase. Within the current range of experimental conditions, we observed a compositional range of P phase of 0.39 < x < 0.81, corresponding to 19-61% dehydrogenation. Increasing temperature and heating time will help release hydrogen and lower x, suggesting that dehydrogenation could be approaching completion at the high-temperature conditions of the lower mantle over extended geological time. Our observations indicate a fundamental change in the mode of hydrogen release from dehydration in the upper mantle to dehydrogenation in the deep lower mantle, thus differentiating the deep hydrogen and hydrous cycles.
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The spin-orbit Mott insulator Sr_{3}Ir_{2}O_{7} provides a fascinating playground to explore insulator-metal transition driven by intertwined charge, spin, and lattice degrees of freedom. Here, we report high-pressure electric resistance and resonant inelastic x-ray scattering measurements on single-crystal Sr_{3}Ir_{2}O_{7} up to 63-65 GPa at 300 K. The material becomes a confined metal at 59.5 GPa, showing metallicity in the ab plane but an insulating behavior along the c axis. Such an unusual phenomenon resembles the strange metal phase in cuprate superconductors. Since there is no sign of the collapse of spin-orbit or Coulomb interactions in x-ray measurements, this novel insulator-metal transition is potentially driven by a first-order structural change at nearby pressures. Our discovery points to a new approach for synthesizing functional materials.
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In this study, first-principle calculations, in situ angle-dispersive X-ray diffraction, and in situ electrical resistance measurements were performed on arsenic telluride (As2Te3) under high pressure. Structural phase transitions and metallized phenomena were observed from the calculated and experimental results. Upon compression, α-As2Te3 transforms into phases α' and αâ³ at â¼5.09 and â¼13.2 GPa, respectively, with two isostructural phase transitions. From 13.2 GPa, As2Te3 starts to transform into phase γ, with one first-order monoclinic to monoclinic crystal structural phase transition. According to the first-principle calculations and electrical resistance measurements, the structural phase transitions in the compression process induce the transformation from an insulator (phase α) across a semimetal (phase α') into a metal (phases αâ³ and γ). The evolution of the structure and transport property upon compression on As2Te3 is helpful for understanding the properties of other A2B3-type compounds under high pressure.
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Materials with an abrupt volume collapse of more than 20 % during a pressure-induced phase transition are rarely reported. In such an intriguing phenomenon, the lattice may be coupled with dramatic changes of orbital and/or the spin-state of the transition metal. A combined inâ situ crystallography and electron spin-state study to probe the mechanism of the pressure-driven lattice collapse in MnS and MnSe is presented. Both materials exhibit a rocksalt-to-MnP phase transition under compression with ca. 22 % unit-cell volume changes, which was found to be coupled with the Mn(2+) (d(5) ) spin-state transition from S=5/2 to S=1/2 and the formation of Mn-Mn intermetallic bonds as supported by the metallic transport behavior of their high-pressure phases. Our results reveal the mutual relationship between pressure-driven lattice collapse and the orbital/spin-state of Mn(2+) in manganese chalcogenides and also provide deeper insights toward the exploration of new metastable phases with exceptional functionalities.
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Hydrostatic pressure, as an alternative of chemical pressure to tune the crystal structure and physical properties, is a significant technique for novel function material design and fundamental research. In this article, we report the phase stability and visible light response of the organolead bromide perovskite, CH3NH3PbBr3 (MAPbBr3), under hydrostatic pressure up to 34 GPa at room temperature. Two phase transformations below 2 GPa (from Pm3Ì m to Im3Ì , then to Pnma) and a reversible amorphization starting from about 2 GPa were observed, which could be attributed to the tilting of PbBr6 octahedra and destroying of long-range ordering of MA cations, respectively. The visible light response of MAPbBr3 to pressure was studied by in situ photoluminescence, electric resistance, photocurrent measurements and first-principle simulations. The anomalous band gap evolution during compression with red-shift followed by blue-shift is explained by the competition between compression effect and pressure-induced amorphization. Along with the amorphization process accomplished around 25 GPa, the resistance increased by 5 orders of magnitude while the system still maintains its semiconductor characteristics and considerable response to the visible light irradiation. Our results not only show that hydrostatic pressure may provide an applicable tool for the organohalide perovskites based photovoltaic device functioning as switcher or controller, but also shed light on the exploration of more amorphous organometal composites as potential light absorber.
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Conventional phase diagram generation involves experimentation to provide an initial estimate of the set of thermodynamically accessible phases and their boundaries, followed by use of phenomenological models to interpolate between the available experimental data points and extrapolate to experimentally inaccessible regions. Such an approach, combined with high throughput first-principles calculations and data-mining techniques, has led to exhaustive thermodynamic databases (e.g. compatible with the CALPHAD method), albeit focused on the reduced set of phases observed at distinct thermodynamic equilibria. In contrast, materials during their synthesis, operation, or processing, may not reach their thermodynamic equilibrium state but, instead, remain trapped in a local (metastable) free energy minimum, which may exhibit desirable properties. Here, we introduce an automated workflow that integrates first-principles physics and atomistic simulations with machine learning (ML), and high-performance computing to allow rapid exploration of the metastable phases to construct "metastable" phase diagrams for materials far-from-equilibrium. Using carbon as a prototypical system, we demonstrate automated metastable phase diagram construction to map hundreds of metastable states ranging from near equilibrium to far-from-equilibrium (400 meV/atom). We incorporate the free energy calculations into a neural-network-based learning of the equations of state that allows for efficient construction of metastable phase diagrams. We use the metastable phase diagram and identify domains of relative stability and synthesizability of metastable materials. High temperature high pressure experiments using a diamond anvil cell on graphite sample coupled with high-resolution transmission electron microscopy (HRTEM) confirm our metastable phase predictions. In particular, we identify the previously ambiguous structure of n-diamond as a cubic-analog of diaphite-like lonsdaelite phase.
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Group V elements in crystal structure isostructural to black phosphorus with unique puckered two-dimensional layers exhibit exciting physical and chemical phenomena. However, as the first element of group V, nitrogen has never been found in the black phosphorus structure. Here, we report the synthesis of the black phosphorus-structured nitrogen at 146 GPa and 2200 K. Metastable black phosphorus-structured nitrogen was retained after quenching it to room temperature under compression and characterized in situ during decompression to 48 GPa, using synchrotron x-ray diffraction and Raman spectroscopy. We show that the original molecular nitrogen is transformed into extended single-bonded structure through gauche and trans conformations. Raman spectroscopy shows that black phosphorus-structured nitrogen is strongly anisotropic and exhibits high Raman intensities in two A g normal modes. Synthesis of black phosphorus-structured nitrogen provides a firm base for exploring new type of high-energy-density nitrogen and a new direction of two-dimensional nitrogen.
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High pressure can drastically alter chemical bonding and produce exotic compounds that defy conventional wisdom. Especially significant are compounds pertaining to oxygen cycles inside Earth, which hold key to understanding major geological events that impact the environment essential to life on Earth. Here we report the discovery of pressure-stabilized divalent ozonide CaO3 crystal that exhibits intriguing bonding and oxidation states with profound geological implications. Our computational study identifies a crystalline phase of CaO3 by reaction of CaO and O2 at high pressure and high temperature conditions; ensuing experiments synthesize this rare compound under compression in a diamond anvil cell with laser heating. High-pressure x-ray diffraction data show that CaO3 crystal forms at 35 GPa and persists down to 20 GPa on decompression. Analysis of charge states reveals a formal oxidation state of -2 for ozone anions in CaO3. These findings unravel the ozonide chemistry at high pressure and offer insights for elucidating prominent seismic anomalies and oxygen cycles in Earth's interior. We further predict multiple reactions producing CaO3 by geologically abundant mineral precursors at various depths in Earth's mantle.
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Carbon-based nanomaterials have exceptional properties that make them attractive for a variety of technological applications. Here, we report on the use of diamondoids (diamond-like, saturated hydrocarbons) as promising precursors for laser-induced high-pressure, high-temperature diamond synthesis. The lowest pressure and temperature (P-T) conditions that yielded diamond were 12 GPa (at ~2000 K) and 900 K (at ~20 GPa), respectively. This represents a substantially reduced transformation barrier compared with diamond synthesis from conventional (hydro)carbon allotropes, owing to the similarities in the structure and full sp3 hybridization of diamondoids and bulk diamond. At 20 GPa, diamondoid-to-diamond conversion occurs rapidly within <19 µs. Molecular dynamics simulations indicate that once dehydrogenated, the remaining diamondoid carbon cages reconstruct themselves into diamond-like structures at high P-T. This study is the first successful mapping of the P-T conditions and onset timing of the diamondoid-to-diamond conversion and elucidates the physical and chemical factors that facilitate diamond synthesis.
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The 6M BaIrO(3) with the distorted hexagonal BaTiO(3) structure was synthesized by high-pressure sintering. Through Rietveld refinement of the powder X-ray diffraction data, the lattice parameters of a = 5.7459(1) A, b = 9.9289(2) A, c = 14.3433(2) A, and beta = 91.340(1) degrees were obtained. In the Ir(2)O(9) dioctahedron, the average Ir-O distance and direct Ir-Ir distance were equal to 2.067(19) and 2.719(1) A, respectively. The temperature dependence of electrical resistivity shows that the 6M BaIrO(3) is a new metallic iridate. It is an abnormal metal, being deviated from the Fermi liquid behavior, following a linear relationship of rho versus T below 20 K. Both magnetic susceptibility and specific heat data indicate that it is an exchange-enhanced Pauli paramagnet, because of the electron-electron correlation effect.
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A drastically altered chemistry was recently discovered in the Fe-O-H system under deep Earth conditions, involving the formation of iron superoxide (FeO2Hx with x = 0 to 1), but the puzzling crystal chemistry of this system at high pressures is largely unknown. Here we present evidence that despite the high O/Fe ratio in FeO2Hx, iron remains in the ferrous, spin-paired and non-magnetic state at 60-133 GPa, while the presence of hydrogen has minimal effects on the valence of iron. The reduced iron is accompanied by oxidized oxygen due to oxygen-oxygen interactions. The valence of oxygen is not -2 as in all other major mantle minerals, instead it varies around -1. This result indicates that like iron, oxygen may have multiple valence states in our planet's interior. Our study suggests a possible change in the chemical paradigm of how oxygen, iron, and hydrogen behave under deep Earth conditions.
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The lithium-air battery has great potential of achieving specific energy density comparable to that of gasoline. Several lithium oxide phases involved in the charge-discharge process greatly affect the overall performance of lithium-air batteries. One of the key issues is linked to the environmental oxygen-rich conditions during battery cycling. Here, the theoretical prediction and experimental confirmation of new stable oxygen-rich lithium oxides under high pressure conditions are reported. Three new high pressure oxide phases that form at high temperature and pressure are identified: Li2O3, LiO2, and LiO4. The LiO2 and LiO4 consist of a lithium layer sandwiched by an oxygen ring structure inherited from high pressure ε-O8 phase, while Li2O3 inherits the local arrangements from ambient LiO2 and Li2O2 phases. These novel lithium oxides beyond the ambient Li2O, Li2O2, and LiO2 phases show great potential in improving battery design and performance in large battery applications under extreme conditions.
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Diamond owes its unique mechanical, thermal, optical, electrical, chemical, and biocompatible materials properties to its complete sp 3-carbon network bonding. Crystallinity is another major controlling factor for materials properties. Although other Group-14 elements silicon and germanium have complementary crystalline and amorphous forms consisting of purely sp 3 bonds, purely sp 3-bonded tetrahedral amorphous carbon has not yet been obtained. In this letter, we combine high pressure and in situ laser heating techniques to convert glassy carbon into "quenchable amorphous diamond", and recover it to ambient conditions. Our X-ray diffraction, high-resolution transmission electron microscopy and electron energy-loss spectroscopy experiments on the recovered sample and computer simulations confirm its tetrahedral amorphous structure and complete sp 3 bonding. This transparent quenchable amorphous diamond has, to our knowledge, the highest density among amorphous carbon materials, and shows incompressibility comparable to crystalline diamond.Diamond's properties are dictated by its crystalline, fully tetrahedrally bonded structure. Here authors synthesize a bulk sp 3-bonded amorphous form of carbon under high pressure and temperature, show that it has bulk modulus comparable to crystalline diamond and that it can be recovered under ambient conditions.
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An organic-inorganic halide CH3 NH3 SnI3 perovskite with significantly improved structural stability is obtained via pressure-induced amorphization and recrystallization. In situ high-pressure resistance measurements reveal an increased electrical conductivity by 300% in the pressure-treated perovskite. Photocurrent measurements also reveal a substantial enhancement in visible-light responsiveness. The mechanism underlying the enhanced properties is shown to be associated with the pressure-induced structural modification.
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High-efficiency red phosphors with non-rare-earth activators are emerging as an alternative for next generation solid-state warm white LEDs. Their optical properties depend strongly on the local site symmetry and the crystal field strength. Herein we present the pressure tuning of structural and photoluminescence (PL) properties of Mn(4+)-doped BaTiF6 up to 40 GPa. In situ high pressure synchrotron X-ray diffraction, Raman and PL spectroscopy studies show that the crystal symmetry changes from trigonal at ambient pressure to monoclinic from 0.5 GPa and triclinic above 14 GPa, attributed to the distortion of (Ti/Mn)F6 octahedra. The red emission peaks shift monotonically to longer wavelengths due to the reinforced crystal field strength within MnF6 octahedra as pressure increases. A detailed comparison of emission shift rate, PL intensity and FWHM between Mn(4+)-doped BaTiF6 and ruby (Cr(3+)-doped Al2O3) was performed using neon pressure transmission medium. This demonstration provides not only an efficient way to artificially tune the emission properties of practically useful phosphors by means of hydrostatic pressure, but also alternative candidates as potential pressure gauges for high pressure techniques.
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Perovskite-structure materials generally exhibit local structural distortions that are distinct from long-range, average crystal structure. The characterization of such distortion is critical to understanding the structural and physical properties of materials. In this work, we combined Pair Distribution Function (PDF) technique with Raman spectroscopy and electrical resistivity measurement to study Bi(Ni1/2Ti1/2)O3 perovskite under high pressure. PDF analysis reveals strong local structural distortion at ambient conditions. As pressure increases, the local structure distortions are substantially suppressed and eventually vanish around 4 GPa, leading to concurrent changes in the electronic band structure and anomalies in the electrical resistivity. Consistent with PDF analysis, Raman spectroscopy data suggest that the local structure changes to a higher ordered state at pressures above 4 GPa.
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A new method for measuring melting temperatures in the laser-heated diamond cell is described. This method circumvents previous problems associated with the sample instability, thermal runaway, and chemical reactions. Samples were heated with a single, 20 milliseconds rectangular pulse from a fiber laser, monitoring their thermal response with a fast photomultiplier while measuring the steady state temperature with a CCD spectrometer. The samples were recovered and analyzed using scanning electron microscopy. Focused ion beam milling allowed to examine both the lateral and the vertical solid-liquid boundaries. Ambient pressure tests reproducibly yielded the known melting temperatures of rhenium and molybdenum. Melting of Re was measured to 50 GPa, a 5-fold extension of previous data. The refractory character of Re is drastically enhanced by pressure, in contrast to Mo.
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Polycrystalline samples of the perovskite family Sr(1-x)Ca(x)CrO(3) have been prepared at high pressure and temperature in steps of 1/6 over the range 0 ≤ x ≤ 1. Rietveld analysis shows a series of structural phase transitions from cubic to tetragonal to orthorhombic with increasing x. The cubic samples have no long-range magnetic order; the other samples become antiferromagnetically ordered below a T(N) that increases with x. At ambient pressure, the electric transport properties of the cubic and tetragonal phases are semiconducting with a small (meV range) activation energy that increases with x; the orthorhombic phase exhibits variable-range hopping rather than the small-polaron behavior typically found for mixed-valent, localized-electron configurations. Above a pressure P=P(C), a smooth insulator-metal transition is found at a T(IM) that decreases with increasing P for a fixed x; P(C) increases with x. These phenomena are rationalized qualitatively with a π(∗)-band model having a width W(π) that approaches crossover from itinerant-electron to localized-electron behavior as W(π) decreases with increasing x. The smaller size of the Ca(2+) ion induces the structural changes and the greater acidity of the Ca(2+) ion is primarily responsible for narrowing W(π) as x increases.