High-pressure Synthesis Method Research Articles

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.

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.

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 synthesis and magnetic characterization of quadruple perovskites SmA′3Co4O12 (A′ = Cu, Mn)

In this study, two novel quadruple perovskite compounds SmA′3Co4O12 (A′ = Cu, Mn) were synthesized using a high-pressure synthesis method. Structural analysis of the perovskites using synchrotron X-ray powder diffraction revealed that both SmCu3Co4O12 and SmMn3Co4O12 have cubic Im3‾ structure. In the temperature range of 2–300 K, SmCu3Co4O12 did not exhibit a magnetic phase transition, whereas SmMn3Co4O12 exhibited a paramagnetic to ferrimagnetic phase transition at ∼90 K. A comparison of structural information, X-ray absorption near edge structure, and magnetic properties revealed that the low-spin state (S = 0) characterizes the spin state of Co3+ when the A′ site is occupied by Cu3+. However, when the A′ site is occupied by Mn3+, the Co3+ spin state is in a high-spin state (S = 2), indicating that a long-range magnetic phase transition occurs owing to the magnetic interaction between the Mn and Co ions.

Preparation of High-Performance Mn-Doped SnTe Materials at High Pressure and High Temperature.

SnTe is an environmentally friendly medium-temperature thermoelectric material, but its inherent low power factor (PF) and high lattice thermal conductivity severely limit its application. In this study, based on the fact that Mn doping can induce band convergence, the high-pressure and high-temperature (HPHT) synthesis method was used to optimize the sample preparation and shorten the synthesis cycle to 30 min. The results show that the Sn0.93Mn0.10Te sample achieves the maximum PF value of 34.00 μW cm-1 K-2 at 775 K and PFave value of 21.36 μW cm-1 K-2 between 300-875 K. Microstructure analysis shows that the high-pressure synthesis method introduces abundant grain boundaries, various grain sizes, multiple defects, and pore structures into the sample. These microscopic crystal structures can effectively scatter phonons and lower the lattice thermal conductivity. The modification of these micromorphologies results in the Sn0.92Mn0.11Te sample attaining a minimum lattice thermal conductivity of 0.45 W m-1 K-1 at 625 K. The thermoelectric figure of merit (zT) of sample Sn0.92Mn0.11Te reaches a maximum value of 1.1 at 775 K, and the zTave reaches 0.63 in the range of 300-875 K. This study indicates that the synergistic effect of Mn element doping and microstructure modification can effectively optimize the thermoelectric transport performance of SnTe materials.

The layered RuBr3–RuI3 honeycomb system

A honeycomb layered Ru(Br1−xIx)3 solid solution is prepared through a high-pressure synthesis method, with anion disorder and strong spin–orbit coupling. Their electronic and magnetic properties vary dramatically with changing chemical composition.

Review of progress in the materials development of Re, Os, and Ir-based double perovskite oxides

In this review, we examine the latest experimental advances in materials science, focusing primarily on 5d transition metal-based double perovskite oxides, particularly rhenium (Re), osmium (Os), and iridium (Ir). These materials have attracted considerable attention because of their unique properties compared to conventional perovskite oxides, including high-TC ferrimagnetism, half-metallicity, insulating ferromagnetism, polar ferroelectricity, and multipolar magnetism. We have shown through many experiments that the high-temperature and high-pressure synthesis method is effective for introducing 5d transition metals such as Re, Os, and Ir into the B site of perovskite oxides. Here, we mainly discuss the high-pressure synthesis of novel double perovskite oxides and their properties. This process leads to characteristic relativistic effects and properties not observed in conventional perovskites. The adaptable nature of the double perovskite structure allows for significant modification of both A- and B-site elements, resulting in a wide range of physical properties. In this review, we will organize our understanding of Re-, Os-, and Ir-based double perovskites, highlight the influence of crystal structure on various properties, and explore potential applications across multiple technical and scientific domains. The goal is to provide a comprehensive overview that will enhance understanding and facilitate advances in the field of double perovskite materials research.

Comparison of Gd addition effect on the superconducting properties of FeSe0.5Te0.5 bulks under ambient and high-pressure conditions

We have prepared a series of (FeSe0.5Te0.5 + xGd) bulk samples, with x = 0, 0.03, 0.05, 0.07, 0.1 and 0.2, through the convenient solid-state reaction method at ambient pressure (CSP). High gas pressure and high-temperature synthesis methods (HP-HTS) are also applied to grow the parent compound (x = 0) and 5 wt% of Gd-added bulks. Structural, microstructural, transport and magnetic characterizations have been performed on these samples in order to draw the final conclusion. Our analysis results that the HP-HTS applied for the parent compound enhances the transition temperature (Tc) and the critical current density (Jc) with the improved sample density and intergrain connections. The lattice parameter ‘c’ is increased with Gd additions, suggesting a small amount of Gd enters the tetragonal lattice of FeSe0.5Te0.5 and the Gd interstitial sites are along the c-axis. A systematic decrease of the onset transition temperature Tc is observed with Gd additions, however, the calculated Jc of these Gd-added samples is almost the same as that of the parent compound prepared by CSP. It specifies that there is no improvement of the grain connections or pinning properties due to these rare earth additions. However, Gd-added FeSe0.5Te0.5 bulks prepared by HP-HTS have revealed a slightly improved critical current density due to improved grain connections and sample density but have a lower transition temperature than that of the parent compounds.

High-Pressure Synthesis and the Enhancement of the Superconducting Properties of FeSe0.5Te0.5.

A series of FeSe0.5Te0.5 bulk samples have been prepared using the high gas pressure and high-temperature synthesis (HP-HTS) method to optimize the growth conditions for the first time and investigated for their superconducting properties using structural, microstructure, transport, and magnetic measurements to reach the final conclusions. Ex situ and in situ processes are used to prepare bulk samples under a range of growth pressures using Ta-tube and without Ta-tube. The parent compound synthesized by convenient synthesis method at ambient pressure (CSP) exhibits a superconducting transition temperature of 14.8 K. Our data demonstrate that the prepared FeSe0.5Te0.5 sealed in a Ta-tube is of better quality than the samples without a Ta-tube, and the optimum growth conditions (500 MPa, 600 °C for 1 h) are favorable for the development of the tetragonal FeSe0.5Te0.5 phase. The optimum bulk FeSe0.5Te0.5 depicts a higher transition temperature of 17.3 K and a high critical current density of the order of >104 A/cm2 at 0 T, which is improved over the entire magnetic field range and almost twice higher than the parent compound prepared using CSP. Our studies confirm that the high-pressure synthesis method is a highly efficient way to improve the superconducting transition, grain connectivity, sample density, and pinning properties of a superconductor.

Single Crystal Growth of Ilmenite-Type MnVO3 by Solid-State Recrystallization

We successfully obtained high-quality single-domain crystals of ilmenite-type MnVO3 under high-pressure and high-temperature conditions (4 GPa and 1173 K for 1–8 h). The maximum crystal size was ∼0.5 mm. Single crystals were grown by solid-state recrystallization near the perovskite–ilmenite phase boundary under high-pressure conditions. Crystal growth occurred without fluxes or water, unlike conventional single crystal growth by high-pressure synthesis methods. Crystal structure refinement revealed that V–V dimers, produced by direct chemical bonding between vanadium ions, existed below 550 K at ambient pressure. The V–V dimerization was accompanied by a structural phase transition from rhombohedral to triclinic ilmenite-type structures. The obtained single crystals can facilitate precise analyses using resonant inelastic X-ray scattering and angle-resolved photoemission spectroscopy, which can reveal the mechanism underlying the phenomenon of V–V dimerization.

Magnetic-atom strategy enables unilamellar MoS2-C interoverlapped superstructure with ultrahigh capacity and ultrafast ion transfer capability in Li/Na/K-ion batteries

Constructing a unilamellar MoS2-C interoverlapped superstructure (UIS) is the most promising way to improve electrical conductivity and alleviate volume expansion of MoS2 electrodes during Li+/Na+/K+ storage due to the maximized atomic interface contact. However, the interlayer distance of ∼ 0.48 nm between MoS2 and C (lower than 0.62 nm of pristine MoS2), the unconspicuous enhancement of intrinsic conductivity of MoS2, and the inevitable decrease in capacity due to the introduced low-capacity C undoubtedly hamper ion transport and storage, thus resulting in limited enhancement of capacity and fast-charging performances of UIS. Herein, we propose a magnetic-atom strategy for UIS via a one-step high-pressure vapor-phase synthesis method, during which the interlayer electrostatic repulsion is in-situ constructed by magnetic-atom Fe and/or Co doping to adjust the interlayer distance from 0.48 to 0.64 nm. In addition, the doped magnetic atom can regulate the electronic structure of UIS to obtain the bandgap of 0 eV to enhance electron transfer. Importantly, the doped magnetic atom can be reduced to superparamagnetic metallic nanoparticles during conversion reactions, which can store abundant spin-polarized electrons to induce strong surface-capacitance effects, thus boosting ion transport and storage. Consequently, the magnetic-atom strategy endows the UIS with ultrahigh reversible capacities of 1572.1/738.5/542.3 mAh/g at 0.1C, 971.2/383.5/209.8 mAh/g at 5C after 3000 cycles, and 761.5/340.8/204.5 mAh/g at 20C as Li/Na/K-ion-battery anodes, respectively. This work verifies the efficiency of magnetic-atom strategy and paves a way for the design of other transition metal dichalcogenides for electrochemical energy storage.

High-pressure A-site manganites: Structures and magnetic properties

Compounds of general formula ABO3 are widely studied due to their versatility regarding chemical composition, structure and physical properties. The use of high-pressure and high-temperature synthesis method allows the introduction of small Mn2+ cation into the often-large A site, giving rise to the so-called A-site manganites, with a few exceptions to this rule. Polymorphism, structural features and magnetic properties of A-site manganites are revisited in this short review dedicated to Miguel A. Alario y Franco on his 80th birthday. We extend this dedication to John B. Goodenough and J. Paul Attfield on their 100th and 60th birthdays in recognition of their ground work. Happy birthday all three!

Synthesis of the Candidate Topological Compound Ni3Pb2.

Spin-orbit coupling enables the realization of topologically nontrivial ground states. As spin-orbit coupling increases with increasing atomic number, compounds featuring heavy elements, such as lead, offer a pathway toward creating new topologically nontrivial materials. By employing a high-pressure flux synthesis method, we synthesized single crystals of Ni3Pb2, the first structurally characterized bulk binary phase in the Ni-Pb system. Combining experimental and theoretical techniques, we examined structure and bonding in Ni3Pb2, revealing the impact of chemical substitutions on electronic structure features of importance for controlling topological behavior. From these results, we determined that Ni3Pb2 completes a series of structurally related transition-metal-heavy main group intermetallic materials that exhibit diverse electronic structures, opening a platform for synthetically tunable topologically nontrivial materials.

V-V Dimerization and Magnetic State of Cobalt Ions in Ilmenite-Type CoVO3.

The nature of chemical bonds determines the electronic and magnetic properties of compounds. A metal-metal bonding (V-V dimer) and its effect on the magnetism of ilmenite-type CoVO3 were studied. Polycrystalline CoVO3 samples were synthesized using a high-pressure synthesis method. Crystal structure refinement revealed that V-V dimers exist at temperatures below 550 K in the vanadium layers. Co2+ in CoVO3 exhibits an S = 3/2 state, whereas a Jeff = 1/2 state was reported in ilmenite-type CoTiO3. The existence of V-V dimers reduces the structural symmetry (from R3 to P1), which can change the magnetic ground state.

Formation of the Metastable Iron (III) Germanate Fe2GeO5 through Kinetic Control of the Oxidative Reaction

Abstract Synthesis of complex oxides requires high temperatures to overcome barriers due to the diffusion of solids. Therefore, the most stable polymorphs are obtained in general reactions. However, it is necessary to design kinetic reactions with low initial energy barriers and control the reaction path and products to synthesize novel and metastable oxides. We report the synthesis of a metastable Fe2GeO5 with a kyanite-type structure via kinetic control of oxidative reaction in Fe2GeO4. It is also found that Fe2GeO5 was not synthesized at all by the conventional method, high-pressure synthesis method, or coprecipitation method. Our result indicates that kinetic control of the oxidative reaction is a promising method for synthesizing metastable materials.

Intrinsically low thermal conductivity of tetragonal-structured PbSe2

Designing new compounds with earth-abundant constituent elements and intrinsically low thermal conductivity are crucial to the development of thermoelectric materials. In this letter, the tetragonal-structured PbSe 2 with extremely low thermal conductivity was prepared by two-step ball milling and high pressure synthesis method. Density functional theory calculation shows that the low thermal conductivity of PbSe 2 is originated from its weak interatomic bonding strength and high lattice vibration anharmonicity. We also found that the carrier concentration of PbSe 2 can be tuned effectively by Ag doping in Pb site, which leads to an enhanced figure of merit. These results indicate that PbSe 2 is a potential candidate as a thermoelectric material. • Tetragonal structured PbSe 2 was synthesized by a high-pressure method. • PbSe 2 behaves an extremal low thermal conductivity. • The carrier concentration and ZT of PbSe 2 was enhanced effectively by Ag doping.

Benefit of high-pressure structure on sodium transport properties: Example with NaFeF3 post-perovskite

In the search of promising Na-ion cathode materials, high-pressure synthesis method was applied to obtain sodium iron fluoride NaFeF3 with the post-perovskite lamellar structure. A two-step synthesis was performed: first, the Pnma orthorhombic perovskite structure NaFeF3 form (or Pv-NaFeF3, GdFeO3 type) was synthesized at 1270 ​K and 7.7 ​GPa, then the Cmcm orthorhombic post-perovskite structure (or pPv-NaFeF3, CaIrO3 type) was obtained using a second step at 700 ​K and 15 ​GPa. The post-perovskite form was stabilized under ambient conditions with a low amount of remaining perovskite phase (5 ​mol%). The Mössbauer analysis of pPv-NaFeF3 was firstly investigated with a paramagnetic structure obtained at 300 and 77 ​K, opposed to Pv-NaFeF3 magnetism reflecting the different [FeF6] polyhedra arrangements. Finally, the sodium migration within the framework of both structures was evaluated with the use of Bond Valence Energy Landscape (BVEL) calculations, resulting with an enhanced Na+ mobility within the pPv-NaFeF3 structure.

Temperature evolution of 3d- and 4f-electron magnetic ordering in the ferrimagnetic Mn self-doped perovskite (Yb0.667Mn0.333)MnO3

A high-pressure synthesis method was employed to prepare Mn-self-doped perovskites (R 0.667Mn0.333)MnO3 (R = Yb, Lu) at about 6 GPa and 1670 K. Crystal and magnetic structures of (Yb0.667Mn0.333)MnO3 have been studied by combining neutron powder diffraction, magnetic susceptibility and specific heat measurements. Within the orthorhombic space group Pnma, magnetic cations are located on site 4c (A site, occupied by two thirds of Yb3+ and one third of Mn2+) and on site 4b (B site, occupied by two thirds of Mn3+ and one third of Mn4+). The degree of structural distortion of the MnO6 octahedra follows the general trend of (R1−x Mn x )MnO3 compounds which shows a decrease with increasing amount of Jahn–Teller inactive Mn4+ cations. Mn–Mn interactions produce a collinear ferrimagnetic structure (T C,Mn = 106 K) with ferromagnetically ordered Mn moments at the B site being coupled antiferromagnetically with ordered Mn moments at the A site. Mn–Yb interactions induce a small but non-zero ferromagnetic Yb3+ moment which can explain a small decrease of the magnetic susceptibility at low temperature. Yb–Yb interactions create an antiferromagnetic structure at T N,Yb ≈ 40 K. Ordered moments of the ferrimagnetic and antiferromagnetic structures are oriented perpendicular to each other within the ac-plane and Yb3+ moments contribute to both structures. The appearance of ordered Yb3+ moments induced by Mn–Yb interactions in perovskite (Yb0.667Mn0.333)MnO3 is a result of the Mn self-doping on the A site and has not been observed in the orthorhombic perovskite modification (space group Pnma) of the undoped parent compound YbMnO3, but interestingly, it also appears in the hexagonal non-perovskite modification (space group P63 cm) of YbMnO3.

Microstructure and thermoelectric properties of α-and γ-Al2O3 doped ZnO under high pressure

Using high pressure and high temperature (HPHT) technology to improve the thermoelectric properties of oxides is a feasible solution. To further understand the micro-physical mechanism improving the thermoelectric performance of ZnO in a higher pressure environment, the effects of α and γ lattice structure Al2O3 (α-Al2O3, γ-Al2O3) on doped ZnO were systematically studied. ZnO samples with different Al doping ratios (α-x, γ-x; x = 0.02, 0.04, 0.06, 0.08) were prepared by HPHT. Test results show that the high pressure and high temperature synthesis method effectively improves the solid solubility of α-Al2O3 and γ-Al2O3 in ZnO, among which γ-Al2O3 is more easily dissolved into the zinc oxide crystal lattice. Under the same doping ratio, the electronic conductivity of the sample synthesized with γ-Al2O3 is higher than that of the sample synthesized with α-Al2O3. In addition, the ZnAl2O4 phase precipitated out of the sample with increased Al doping. Although the ZnAl2O4 phase decreases the electrical properties of the sample, a small amount of ZnAl2O4 is uniformly dispersed in the ZnO sample, which can inhibit the growth of crystal grains, and assist grain refinement. The optimized high pressure sintering temperature was 1123 K, and the zT value of γ-0.04 was 0.17 at 973 K.

Magnetic properties and ferrimagnetic structures of Mn self-doped perovskite solid solutions (Ho1−xMnx)MnO3

A high-pressure synthesis method was employed to prepare (Ho1-xMnx)MnO3 solid solutions with x = 0.2 and 0.3 (at about 6 GPa and 1,670 K) and magnetic properties and structures were investigated by magnetic, dielectric and neutron diffraction measurements. Both samples crystallize in the GdFeO3-type Pnma perovskite structure, and both samples show magnetization reversal behavior below the compensation temperature of about 35 K (at H = 100 Oe). The magnetization reversal phenomena are originated from a ferrimagnetic (FiM) structure which takes place below TC = 76 K (x = 0.2) and 102 K (x = 0.3) and is built from ferromagnetic (FM) ordering of Mn3+ and Mn4+ cations at the B site which are antiferromagnetically (AFM) coupled with Ho3+ and Mn2+ cations at the A site. The magnetic moment of Ho3+ cations increases significantly with deceasing temperature, and it overcomes the saturated magnetic moment of Mn3+ and Mn4+ cations at the B site. Field-induced first-order transitions were found in both compounds below about 35 K. Neutron diffraction measurements on the x = 0.2 sample found a collinear FiM structure between 76 K and 40 K, and the development of spin canting at the A site below 40 K. The coexistence of Ho3+ and Mn2+ at the A-site gives rise to additional short-range magnetic ordering of Ho3+ and to strain effects along the a-direction which are stronger than in (R1−xMnx)MnO3 materials with heavier and smaller rare-earths cations.