High-pressure Synthesis Research Articles

A New High-Pressure High-Temperature Phase of Silver Antimonate AgSbO3 with Strong Ag-O Hybridization.

We report on a new polymorph of silver antimonate AgSbO3 discovered with the use of high-pressure high-temperature synthesis at 16 GPa and 1380 °C. The crystal structure is determined from X-ray powder diffraction, and we find this new high-pressure phase crystallizes in monoclinic space group C2/c with the following values: a = 8.4570(3) Å, b = 9.8752(3) Å, c = 8.9291(3) Å, β = 91.1750(12)°, and V = 745.56(4) Å3. We synthesized the high-pressure (16 GPa) AgSbO3 phase from the ilmenite phase as a precursor. This high-pressure monoclinic AgSbO3 consists of a three-dimensional network of corner- and edge-sharing SbO6 octahedra with channels along the c-direction containing Ag atoms. We also synthesize AgSbO3 in the defect pyrochlore phase at 4 GPa from the same ilmenite precursor and compare the Raman spectra and the cation-anion bonding of all three AgSbO3 phases. The absence of a cubic perovskite form of AgSbO3 even at pressures of ≤16 GPa is likely due to the covalency of the Sb-O bonds and the moderate electronegativity of Ag+. Hybridization of Ag d and O p orbitals results in a variation of Ag-O distances that correlates with the band gap, which is in qualitative agreement with the density of states around the Fermi level from our density functional calculations. We compare AgSbO3 with other ABX3 compounds to elucidate the dependence of the structure on the constituent atoms.

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.

High-Pressure Synthesis of Te-Ge Double-Substituted Skutterudite with Enhanced Thermoelectric Properties.

We synthesized Co4Sb11TexGe1-x (x = 0.5-0.8) using high-pressure, high-temperature conditions at ∼2 GPa and ∼900 K. The microstructure, morphology, and components were characterized via X-ray diffraction, scanning electron microscopy, and electron backscatter diffraction (EBSD). EBSD indicated that the average grain size of Co4Sb11Te0.8Ge0.2 was 1 μm. Electrical conductivity, Seebeck coefficient, and thermal conductivity were measured from 300 to 800 K. The minimum lattice thermal conductivity of Co4Sb11Te0.8Ge0.2 was 0.72 W m-1 K-1, 74% lower than that at 300 K. The introduction of Te and Ge effectively enhanced point effects scattering and location scattering, notably decreasing lattice thermal conductivity. Therefore, the maximum zT value of Co4Sb11Te0.8Ge0.2 was 1.13 at 800 K. These results indicate that high pressure combined with multielement substitution optimized the thermoelectric transport properties of skutterudites.

High-pressure synthesis and characterizations of a new ternary Ce-based compound Ce3TiAs5

We report the structure and properties of a new Ce-based compound Ce3TiAs5synthesized under high-pressure and high-temperature conditions. It crystallizes in a hexagonal Hf5Sn3Cu-anti type structure with zig-zag like Ce chains along thecaxis. This compound is metallic and undergoes a magnetic phase transition atTN= 13 K. A metamagnetic transition occurs at ∼0.7 T. The Sommerfeld coefficient for the compound is determined to be about 215 mJ/(Ce-mol*K2), demonstrating a heavy Fermion behavior. The resistivity is featured with two humps, which arises from the synergistic effect of crystal electric field and magnetic scattering. The magnetic ordering temperatureTNgradually increases in the sequence of Ce3TiPn5with Pn = Bi, Sb, and As, which implies that the Ruderman-Kittel-Kasuya-Yosida interaction should be still predominant in Ce3TiAs5.

Macroscopic perspective on phase transition behavior of natural single-crystal graphite under different pressure environments

Comprehensive understanding of the direct transformation pathway from graphite to diamond under high temperature and high pressure has long been one of the fundamental goals in materials science. Despite considerable experimental and theoretical progress, current experimental studies have mainly focused on the local microstructural characterizations of recovered samples, which has certain limitations for high-temperature and high-pressure products, which often exhibit diversity. Here, we report on the pressure-induced phase transition behavior of natural single-crystal graphite under three distinct pressure-transmitting media from a macroscopic perspective using in situ two-dimensional Raman spectroscopy, scanning electron microscopy, and atomic force microscopy. The surface evolution process of graphite before and after the phase transition is captured, revealing that pressure-induced surface textures can impede the continuity of the phase transition process across the entire single crystal. Our results provide a fresh perspective for studying the phase transition behavior of graphite and greatly deepen our understanding of this behavior, which will be helpful in guiding further high-temperature and high-pressure syntheses of carbon allotropes.

High pressure-derived nonsymmetrical [Cu2O]2+ core for room-temperature methane hydroxylation.

Nonsymmetrical oxygen-bridged binuclear copper centers have been proposed and modeled as intermediates and transition states in several C─H oxidation pathways, leading to the postulation that structural dissymmetry enhances the reactivity of the bridging oxygen. However, experimentally characterizing the structure and reactivity of these transient species is remarkably challenging. Here, we report the high-pressure synthesis of a metastable nonsymmetrical dicopper-μ-oxo compound with exceptional reactivity toward the mono-oxygenation of aliphatic C─H bonds. The nonequivalent coordination environment of copper stabilizes localized mixed valency and greatly enhances the hydrogen atom abstraction activity of the bridging oxygen, enabling room-temperature hydroxylation of methane under pressure. These findings highlight the role of dissymmetry in the reactivity of binuclear copper centers and demonstrate precise control of molecular structures by mechanical means.

High-pressure synthesis, mechanical properties, and oxidation behavior of advanced boron-containing α/β-Si 3N 4/Si ceramics using polymer-derived amorphous SiBN ceramics

High-pressure synthesis, mechanical properties, and oxidation behavior of advanced boron-containing α/β-Si ₃N ₄/Si ceramics using polymer-derived amorphous SiBN ceramics

Rapid Synthesis of Sb2Si2Te6 under High Pressure with a Modulated Microstructure.

Over the past decades, thermoelectric materials have advanced significantly, yet materials such as Sb2Si2Te6, which are challenging to synthesize chemically, often require lengthy and complex preparation processes, hindering their development. In this work, we prepare polycrystalline Sb2Si2Te6 bulk from elemental precursors using a high-pressure synthesis (HPS) method. This method offers significant advantages in efficiency and preparation duration. The applied pressure promotes an isotropic microstructure and regulates the thermoelectric properties by controlling precipitate contents, grain size, and twinning. Although an increase in thermal conductivity, mostly due to the notable increase in electrical conductivity, leads to less favorable thermal conductivity near room temperature compared to samples prepared using conventional methods, a beneficial reversal occurs at high temperatures. The polycrystalline Sb2Si2Te6 sample synthesized at 2 GPa demonstrates a peak ZT value of 1.1 at 773 K, outperforming most pristine Sb2Si2Te6 materials. This work demonstrates an efficient strategy for optimizing Sb2Si2Te6 performance and offers a new synthesis pathway for other challenging thermoelectric materials.

High-pressure synthesis, crystal structure and anisotropic thermal/compressive behaviors of pseudo-ternary (V,Cr,Mo)P4

Pseudo-ternary CrP4-type (V,Cr,Mo)P4 was successfully synthesized at the conditions of 4 GPa and 900 °C by using a large volume multi-anvil-type press. SEM-EDS and STEM analyses revealed that the synthesized pseudo-ternary (V,Cr,Mo)P4 contains almost equimolar amounts of transition metals. The lattice parameters and unit cell volume of (V,Cr,Mo)P4 yield the average value of its end-members. The low-temperature (133 K–333 K) in-situ synchrotron XRD measurements demonstrated that the c-axis showed the highest coefficient of thermal expansion, followed by the b-axis and the a-axis. These thermal behaviors are the same as the binary end-members and pseudo-binary (V,Cr)P4. While from the high-pressure (P < 10 GPa) in-situ synchrotron XRD measurements, it was found that (V,Cr,Mo)P4 showed no phase transition and compression behaviors in which the c-axis was more compressible than the other two axes (b and a) and the b-axis was slightly compressible more than the a-axis. The zero-pressure bulk modulus of 106 (1) GPa and 122.1 (7) GPa were obtained for (V,Cr)P4 and (V,Cr,Mo)P4, respectively. MoP6 octahedral is highly distorted in comparison with VP4 and CrP4, thus the incorporation of MoP4 greatly yields incompressible behaviors of CrP4-type phosphides with respect to temperature and pressure.

Optimization of Co4Sb11.5Te0.5 thermoelectric performance through Al filling under high temperature and high pressure

So far, the method of optimizing the thermoelectric properties of skutterudite CoSb3 is usually to achieve a breakthrough in high-properties thermoelectric merit by selecting excellent doping atoms and determining a reasonable percentage of atoms. In this study, we achieved the preparation of small atomic radius Al-filled Co4Sb11.5Te0.5 compounds by high-temperature and high-pressure (HTHP) synthesis methods. The thermoelectric properties of the samples AlxCo4Sb11.5Te0.5 were optimized from two dimensions: synthesis pressures (1.0 GPa, 1.5 GPa, 2.0 GPa) and Al filling concentration (x = 0.1, 0.2, 0.3, 0.5), ultimately achieving effective decoupling of electron-phonon transport properties. The experimental results show that Al doping can optimize the electrical transport properties of materials effectively, rapid synthesis method of HTHP can introduce abundant grain boundaries, diversification of grain sizes, a large number of dislocations and widely distributed nano second phase, etc. These microstructures in bulk materials form a multi-scale phonon scattering network in situ, which can effectively scatter phonons and reduce the lattice thermal conductivity effectively. After optimizing the synthesis pressure and Al filling concentration through orthogonal transformation, the sample Al0.3Co4Sb11.5Te0.5 prepared at a synthesis pressure of 1.5 GPa obtained a minimum lattice thermal conductivity value of 0.88 W m−1 K−1, a maximum power factor of 40.96 μ W cm−1 K−2 and a maximum zT value of 1.18 at 773.15 K.

High-pressure synthesis, structure and physical properties of two quasi-one-dimensional compounds Ba9Nb2.54Te15 and Ba9Ta1.89Te15

Two quasi-one-dimensional compounds Ba9Nb2.54Te15 and Ba9Ta1.89Te15 were synthesized under high pressure and high temperature conditions and systematically characterized by structural, transport and magnetic measurements. Both the two compounds crystallize into a hexagonal structure with the space group P-6c2 (No. 188). The structure consists of trimeric face-sharing octahedral Nb/TaTe6 chains separated by a large distance (>10 Å), thus presenting a strong one-dimensional crystal structure. The transport properties suggest that both the two compounds are semiconductors with a band gap ∼ 0.15 eV for Ba9Nb2.54Te15 and ∼ 0.22 eV for Ba9Ta1.89Te15. Magnetic properties characterization indicates that Ba9Nb2.54Te15 displays no long-range-order above 2 K, but with an effective moment μeff ∼ 1.8 μB/f.u., while Ba9Ta1.89Te15 exhibits a diamagnetic behavior. Our results demonstrate that, in the sequence of Ba9V3Te15, Ba9Nb2.54Te15 and Ba9Ta1.89Te15, the occupation in the transition metal sites decreases, the semiconducting band gap increases, and the magnetism changes from ferromagnetism to diamagnetism.

Impact of Synthesis Method on the Structure and Function of High Entropy Oxides.

The term sample dependence describes the troublesome tendency of nominally equivalent samples to exhibit different physical properties. High entropy oxides (HEOs) are a class of materials where sample dependence has the potential to be particularly profound due to their inherent chemical complexity. In this work, we prepare a spinel HEO of identical nominal composition by five distinct methods, spanning a range of thermodynamic and kinetic conditions: solid state, high pressure, hydrothermal, molten salt, and combustion syntheses. By structurally characterizing these five samples across all length scales with a variety of X-ray methods, we find that while the average structure is unaltered, the samples vary significantly in their local structures and their microstructures. The most profound differences are observed at intermediate length scales, both in terms of crystallite morphology and cation homogeneity. As revealed by X-ray fluorescence microscopy ideal cation homogeneity is achieved only in the case of combustion synthesis. These structural differences in turn significantly alter the observed functional properties, which we demonstrate via characterization of their magnetic response. While ferrimagnetic order is retained across all five samples, the sharpness of the transition, the size of the saturated moment, and the coercivity all show marked variations with synthesis method. We conclude that the chemical flexibility inherent to HEOs is complemented by strong synthesis method dependence, providing another axis along which to optimize these materials for a wide range of applications.

High-pressure synthesis of fully dense polymer-derived SiCN ceramics: Structural evolution and mechanical properties

This study explored the microstructural evolution and mechanical behavior of dense amorphous SiCN ceramics by consolidating the PDCs-SiCN powder through high-pressure sintering at different temperatures. The results indicate that the SiCN ceramics remain in an amorphous state under pressures of 5 GPa and temperatures below 1200 ℃. As the temperature increases, the density increases steadily while the porosity decreases, exhibiting excellent properties with a porosity of 0.208 %, hardness and elastic modulus of 26.04±1.29 GPa and 223.8±6 GPa, respectively. As the temperature increases further, the amorphous three-dimensional network deteriorates, leading to a phase transition from amorphous to crystalline. This simultaneous presence of amorphous and crystalline phases can result in an increased formation of pores in ceramics. Precipitation of the soft phase “graphite” and the appearance of high porosity significantly diminish the mechanical properties of bulk ceramics. The high-pressure method represents an attractive avenue for the development of high-performance amorphous Si-based composite ceramics.

Electroluminescent white quantum dot light-emitting diodes based on high pressure synthesis of graphitic C3N4 semiconductor

Graphitic carbon nitride (g-C3N4) has shown promising potentials for quantum dot light-emitting diodes (QLEDs), which might be an effective alternative of the mostly used Cd(Se,S)/Zn(S,Se) emitting layers and can achieve both low toxicity and high stability, meeting the goal of sustainable development. Herein, we for the first report a white electroluminescent QLED device with blue and orange dual-color emissions, which were attributed to the σ*-LP, π*- π, and π*-LP transitions, respectively, from a single-compound g-C3N4 quantum dots (QDs) by synthesizing the precursor at 0.8 Mpa high-pressure N2. By selectively exciting the δ and π bonds with X-ray, the luminescence mechanism was approved with the synchrotron radiation techniques of X-ray absorption near edge structure (XANES) and the X-ray excited optical luminescence (XEOL).The chromaticity coordinate changes from cayan color space with CIE (0.2034, 0.1939) to white color space with CIE (0.3009, 0.2697) as pressure increases from 0.06 to 0.8 Mpa, with the increased overlap of the δ* and π* orbital upon the contraction of crystal lattice. The breakthrough achieved in this work will promisingly promote the development of future white light sources as thin as paper for human home and office lighting by using direct current-driven electroluminescence of QDs, instead of photoluminescence of phosphors.

Effect of high pressure synthesis conditions on the formation of high entropy oxides

High entropy materials are often entropy stabilized, meaning that the configurational entropy from multiple elements sharing a single lattice site stabilizes the structure. In this work, we study how high-pressure synthesis conditions can stabilize or destabilize a high entropy oxide (HEO). We study the high-pressure and high-temperature phase equilibria of two well-known families of HEOs: the rock salt structured compound (Mg,Co,Ni,Cu,Zn)O, including some cation substitutions, and the spinel structured compound (Cr,Mn,Fe,Co,Ni)3O4. Syntheses were performed at various temperatures, pressures, and oxygen activity levels, resulting in dramatically different synthesis outcomes. In particular, in the rock salt HEO, we observe the competing tenorite and wurtzite phases and the possible formation of a layered rock salt phase while the spinel HEO is highly susceptible to partial decomposition into a mixture of rock salt and corundum phases. At the highest tested pressures, 15 GPa, we discover the transformation of the spinel HEO into a metastable modified ludwigite-type structure with the nominal formula (Cr,Mn,Fe,Co,Ni)4O5. The relationship between the synthesis conditions and the final reaction product is not straightforward. Nonetheless, we conclude that high-pressure conditions provide an important opportunity to synthesize high entropy phases that cannot be formed any other way.

High-Pressure Synthesis and Recovery of Single Crystals of the Metastable Manganese Carbide, MnCx.

Transition metal carbides find widespread use throughout industry due to their high strength and resilience under extreme conditions. However, they remain largely limited to compounds formed from the early d-block elements, since the mid-to-late transition metals do not form thermodynamically stable carbides. We report here the high-pressure bulk synthesis of large single crystals of a novel metastable manganese carbide compound, MnCx (P63/mmc), which adopts the anti-NiAs-type structure with significant substoichiometry at the carbon sites. We demonstrate how synthesis pressure modulates the carbon loading, with ~40 % occupancy being achieved at 9.9 GPa.

High-pressure synthesis of Ruddlesden-Popper nitrides.

Layered perovskites with Ruddlesden-Popper-type structures are fundamentally important for low-dimensional properties, for example, photovoltaic hybrid iodides and superconducting copper oxides. Many such halides and oxides are known, but analogous nitrides are difficult to stabilize due to the high cation oxidation states required to balance the anion charges. Here we report the high-pressure synthesis of three single-layer Ruddlesden-Popper (K2NiF4 type) nitrides-Pr2ReN4, Nd2ReN4 and Ce2TaN4-along with their structural characterization and properties. The R2ReN4 materials (R = Pr and Nd) are metallic, and Nd2ReN4 has a ferromagnetic Nd3+ spin order below 15 K. Thermal decomposition gives R2ReN3 with a Peierls-type distortion and chains of Re-Re multiply bonded dimers. Ce2TaN4 has a structural transition driven by octahedral tilting, with local distortions and canted magnetic Ce3+ order evidencing two-dimensional Ce3+/Ce4+ charge ordering correlations. Our work demonstrates that Ruddlesden-Popper nitrides with varied structural, electronic and magnetic properties can be prepared from high-pressure synthesis, opening the door to related layered nitride materials.

Effect of HPHT technology and Se doping on thermoelectric properties of In filled Fe doped CoSb3 materials

Skutterudite (CoSb3) is a kind of promising environment-friendly medium-temperature thermoelectric material. Indium-filled CoSb3 has been widely studied, but its bipolar effect, which is commonly generated between 600 and 700 K, seriously hinders the increase of Seebeck coefficient and zT value. The zT value not only directly reflects the overall thermoelectric performance of the material, but also reflects the thermoelectric conversion efficiency of the device. In this work, In filled and Fe, Se double doped CoSb3 materials were successfully prepared by high-temperature and high-pressure synthesis method (HPHT), with a significant shorten synthesis time of 30 mins for each sample. This research has shown that after Se doping via HPHT synthesis method, the bipolar effect of In-filled CoSb3 was significantly suppressed, thus the temperature limitations of electrical transport performance has been overcome. Through the further microstructure analysis, it was found that the crystal structure of sample In0.5Fe0.01Co3.99Sb11.91Se0.09 has the characteristics of multiple grain sizes and complex defect types. And these two microscopic morphological characteristics resulted in the sample obtaining a minimum lattice thermal conductivity of 0.94 Wm−1K−1 at a test temperature of 773.15 K. Through synergistic optimization of synthesis methods and element substitution, the maximum zT value of 1.21 of the sample In0.5Fe0.01Co3.99Sb11.91Se0.09 has been found at 773.15 K.

High-pressure high-temperature synthesis and characterization of B10C

The boron-rich boron carbide materials have been traditionally synthesized by adding boron powder to B4C material and subjecting it to hot pressing sintering for materials composition containing 8.8–20 at. % carbon in boron (composition range of B10.4C to B4C). Our study explores a synthesis route for B10C starting from high-purity boron and carbon and direct conversion under high pressure and high temperature (HPHT) conditions of 2000 °C and 6–8 GPa. Synthesis was verified via x-ray diffraction analysis, showing the conversion of the high-purity boron and carbon powder mixture into a hexagonal B10C structure (R-3m space group) with lattice parameters of a = b = 5.6115 Å and c = 12.197 Å. The concentration of boron was measured through x-ray photoelectron spectroscopy, confirming the B10C ratio. The measured nanoindentation mean hardness of B10C was 40 GPa. Raman spectroscopy of the HPHT synthesized sample shows characteristic vibrational breathing modes of boron icosahedron and an additional intense band at a vibrational frequency of 380 cm−1. This Raman band, which appears notably weaker in earlier studies and B4C samples, is assigned to the linear chain of B–B–B and attributed to the maximal incorporation of boron within the hexagonal structure.