High-pressure Raman Spectroscopy Research Articles

A search for pressure-induced phase transition in the layered perovskite-like Pr2Ti2O7

In our study, we present comprehensive findings on the structural properties of Pr2Ti2O7 across a broad pressure range of 0-30GPa. Neutron diffraction experiments, conducted under ambient conditions, offer crucial structural insights into the initial monoclinic phase with the P21 space group. As pressure increased, a significant phase transition to the monoclinic P21/m phase occurred at 13.8GPa. Structural data analysis from X-ray diffraction highlights the essence of this transition, identifying it as the tilting of Ti-O6 octahedra. High-pressure Raman spectroscopy data unequivocally confirms the phase transition, detecting anomalies in the baric dependencies of some vibration modes of Pr2Ti2O7 and the emergence of new modes in the Raman spectra within the pressure region associated with the phase transition. The analysis of these novel vibration modes points to alterations in the Ti-O6 octahedra, emphasizing the pivotal role played by Ti4+ and O2- ions in the mechanism of the pressure-driven phase transition.

Pressure-Tunable Large Anomalous Hall Effect in Ferromagnetic Metal LiMn6Sn6

Recently, giant intrinsic anomalous Hall effect (AHE) has been observed in the materials with kagome lattice. Here, we systematically investigate the influence of high pressure on the AHE in the ferromagnet LiMn6Sn6 with clean Mn kagome lattice. Our in situ high-pressure Raman spectroscopy indicates that the crystal structure of LiMn6Sn6 maintains a hexagonal phase under high pressures up to 8.51 GPa. The anomalous Hall conductivity (AHC) σxyA remains around 150 Ω−1⋅cm−1, dominated by the intrinsic mechanism. Combined with theoretical calculations, our results indicate that the stable AHE under pressure in LiMn6Sn6 originates from the robust electronic and magnetic structure.

Negative Linear Compressibility and Interlayer Gap Closure in Layered Rare-Earth Hydroxyhalide (YCl(OH)2) under High Pressure.

Layered materials have attracted extensive attention due to their exceptional physical and chemical properties. Understanding the structural evolution of such materials under high pressure is crucial for the development of new functional materials. In this study, the structure evolution of the synthesized layered rare-earth hydroxyhalide YCl(OH)2 under high pressures up to approximately 9.4 GPa was explored by using a diamond anvil cell combined with synchrotron single-crystal X-ray diffraction. Simultaneously, high-pressure Raman spectroscopy experiment was conducted to 10.3 GPa. Our findings indicate that YCl(OH)2 maintains its symmetry within the experimental pressure range. The pressure-volume data of YCl(OH)2 were fitted to the third-order Birch-Murnaghan equation of state (EoS) to derive its EoS parameters including zero-pressure unit-cell volume (VT0), isothermal bulk modulus (KT0), and its pressure derivative (K'T0): VT0 = 142.47 (1) Å3, KT0 = 38.2 (18) GPa, and K'T0 = 9.8 (1). However, the unit-cell parameters a, b, and c exhibit a distinct compressional behavior, with the a-axis being the most compressible and the b-axis being the least. Particularly noteworthy is the observation that YCl(OH)2 displays a negative linear compressibility along the b-axis within the pressure range of 0.4-5.3 GPa. Further detailed structure refinement and Raman spectroscopy analyses indicate that the anomalous behavior of the b-axis could be attributed to the formation of the O-H···O hydrogen bonding chains along the b direction. Moreover, the coordination number of Y3+ increased from 8 to 9 as the pressure reached 5.3 GPa due to the reduction of the interlayer spacing upon compression, ultimately leading to the closure of the interlayer gap.

High pressure raman spectroscopy and X-ray diffraction of K2Ca(CO3)2 bütschliite: multiple pressure-induced phase transitions in a double carbonate

The crystal structure and bonding environment of K2Ca(CO3)2 bütschliite were probed under isothermal compression via Raman spectroscopy to 95 GPa and single crystal and powder X-ray diffraction to 12 and 68 GPa, respectively. A second order Birch-Murnaghan equation of state fit to the X-ray data yields a bulk modulus, K0=46.9\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${K}_{0}=46.9$$\\end{document} GPa with an imposed value of K0′=4\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${K}_{0}^{\\prime}= 4$$\\end{document} for the ambient pressure phase. Compression of bütschliite is highly anisotropic, with contraction along the c-axis accounting for most of the volume change. Bütschliite undergoes a phase transition to a monoclinic C2/m structure at around 6 GPa, mirroring polymorphism within isostructural borates. A fit to the compression data of the monoclinic phase yields V0=322.2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${V}_{0}=322.2$$\\end{document} Å3,\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$,$$\\end{document}K0=24.8\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${K}_{0}=24.8$$\\end{document} GPa and K0′=4.0\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${K}_{0}^{\\prime}=4.0$$\\end{document} using a third order fit; the ability to access different compression mechanisms gives rise to a more compressible material than the low-pressure phase. In particular, compression of the C2/m phase involves interlayer displacement and twisting of the [CO3] units, and an increase in coordination number of the K+ ion. Three more phase transitions, at ~ 28, 34, and 37 GPa occur based on the Raman spectra and powder diffraction data: these give rise to new [CO3] bonding environments within the structure.

Barocaloric Effects in Dialkylammonium Halide Salts.

Barocaloric effects─solid-state thermal changes induced by the application and removal of hydrostatic pressure─offer the potential for energy-efficient heating and cooling without relying on volatile refrigerants. Here, we report that dialkylammonium halides─organic salts featuring bilayers of alkyl chains templated through hydrogen bonds to halide anions─display large, reversible, and tunable barocaloric effects near ambient temperature. The conformational flexibility and soft nature of the weakly confined hydrocarbons give rise to order-disorder phase transitions in the solid state that are associated with substantial entropy changes (>200 J kg-1 K-1) and high sensitivity to pressure (>24 K kbar-1), the combination of which drives strong barocaloric effects at relatively low pressures. Through high-pressure calorimetry, X-ray diffraction, and Raman spectroscopy, we investigate the structural factors that influence pressure-induced phase transitions of select dialkylammonium halides and evaluate the magnitude and reversibility of their barocaloric effects. Furthermore, we characterize the cyclability of thin-film samples under aggressive conditions (heating rate of 3500 K s-1 and over 11,000 cycles) using nanocalorimetry. Taken together, these results establish dialkylammonium halides as a promising class of pressure-responsive thermal materials.

The curious case of proton migration under pressure in the malonic acid and 4,4'-bipyridine cocrystal.

In the search for new active pharmaceutical ingredients, the precise control of the chemistry of cocrystals becomes essential. One crucial step within this chemistry is proton migration between cocrystal coformers to form a salt, usually anticipated by the empirical ΔpKa rule. Due to the effective role it plays in modifying intermolecular distances and interactions, pressure adds a new dimension to the ΔpKa rule. Still, this variable has been scarcely applied to induce proton-transfer reactions within these systems. In our study, high-pressure X-ray diffraction and Raman spectroscopy experiments, supported by DFT calculations, reveal modifications to the protonation states of the 4,4'-bipyridine (BIPY) and malonic acid (MA) cocrystal (BIPYMA) that allow the conversion of the cocrystal phase into ionic salt polymorphs. On compression, neutral BIPYMA and monoprotonated (BIPYH+MA-) species coexist up to 3.1 GPa, where a phase transition to a structure of P21/c symmetry occurs, induced by a double proton-transfer reaction forming BIPYH22+MA2-. The low-pressure C2/c phase is recovered at 2.4 GPa on decompression, leading to a 0.7 GPa hysteresis pressure range. This is one of a few studies on proton transfer in multicomponent crystals that shows how susceptible the interconversion between differently charged species is to even slight pressure changes, and how the proton transfer can be a triggering factor leading to changes in the crystal symmetry. These new data, coupled with information from previous reports on proton-transfer reactions between coformers, extend the applicability of the ΔpKa rule incorporating the pressure required to induce salt formation.

Realizing Persistent Zero Area Compressibility over a Wide Pressure Range in Cu2 GeO4 by Microscopic Orthogonal-Braiding Strategy.

Zero area compressibility (ZAC) is an extremely rare mechanical response that exhibits an invariant two-dimensional size under hydrostatic pressure. All known ZAC materials are constructed from units in two dimensions as a whole. Here, we propose another strategy to obtain the ZAC by microscopically orthogonal-braiding one-dimensional zero compressibility strips. Accordingly, ZAC is identified in a copper-based compound with a planar [CuO4 ] unit, Cu2 GeO4 , that possesses an area compressibility as low as 1.58(26) TPa-1 over a wide pressure range from ≈0 GPa to 21.22 GPa. Based on our structural analysis, the subtle counterbalance between the shrinkage of [CuO4 ] and the expansion effect from the increase in the [CuO4 ]-[CuO4 ] dihedral angle attributes to the ZAC response. High-pressure Raman spectroscopy, in combination with first-principles calculations, shows that the electron transfer from in-plane bonding dx 2 -y 2 to out-of-plane nonbonding dz 2 orbitals within copper atoms causes the counterintuitive extension of the [CuO4 ]-[CuO4 ] dihedral angle under pressure. Our study provides an understanding on the pressure-induced structural evolution of copper-based oxides at an electronic level and facilitates a new avenue for the exploration of high-dimensional anomalous mechanical materials.

Raman Spectroscopic Study of Ruddlesden—Popper Tetragonal Sr2VO4

The lattice dynamics of tetragonal Sr2VO4 with a Ruddlesden—Popper-layered crystal structure was studied via Raman spectroscopy. We observed three of the four expected Raman-active modes under ambient conditions. Mode Grüneisen parameters and the implicit fractions of two A1g Raman-active modes were determined from high-pressure and high-temperature Raman spectroscopy experiments. The low-energy A1g Raman-active mode involving Sr motions along the c direction has a large isothermal Grüneisen parameter about seven times larger than that of the high-energy A1g Raman-active mode involving apical O motions along the c direction and is, therefore, more anharmonic. The thermodynamic Grüneisen parameter is significantly smaller in Sr2VO4 than in Sr2TiO4 due to the smaller Grüneisen parameter of the high-energy A1g Raman-active mode and other vibrational modes that still need to be identified. The explicit contribution of the low-energy A1g Raman-active mode is negative, and the implicit contribution due to volume change is much larger. Both volume implicit and anharmonic explicit contributions of the high-energy A1g Raman-active mode have similar positive values. The Raman experiment in the air shows that Sr2VO4 begins to decompose above 200 °C.

High-pressure Raman spectroscopy study of α-quartz-like Si1-xGexO2 solid solution

Spontaneous α-Si1-xGexO2 single crystals were synthesized using the set of crystal growth techniques: hydrothermal (XGe = 0.09, 0.20), flux (XGe = 0.45, 0.70) and recycling (XGe = 0.96). The XRD and spectroscopic studies with non-negative matrix factorization show linear dependences of structural parameters and Raman shift on germanium content and confirmed the existence of a complete series of α-Si1-xGexO2 solid solution. The synthesized samples of the solid solution were studied by Raman spectroscopy at the ambient conditions and for the first time at high pressures up to ∼30 GPa. The obtained results suggest a phase transition “α-quartz → post-quartz” for Si1-xGexO2 in the examined pressure range. The formation of the possible intermediate phase (quartz-II) was detected for Si1-xGexO2 with XGe = 0.09, 0.20 and 0.45 at 11, 10 and 7.5 GPa, respectively. The linear dependences of the pressure value of phase transitions on germanium content were observed. At decompression, the post-quartz phase remained stable that was determined by Raman spectra for all compositions of solid solution. Obtained experimental results revealed the correlation of the chemical composition, spectroscopic characteristics, and structural deformations at ambient conditions and at high pressures.

An insight into microstructure and structure stability of Ni-doped Bi2212 ceramics

A series of Bi2Sr2-xNixCaCu2O8+δ (x = 0.00, 0.10, 0.20 and 0.30) ceramics samples were synthesized by Pechini sol-gel method. In this work, the microstructure and structure stability of Ni-doped Bi2212 system were investigated particularly by X-ray diffraction, electron microscopy and high-pressure Raman spectroscopy. It is confirmed that the main phase of all samples is the typical Bi2212 tetragonal phase with space group I4/mmm. As Ni-doping amount x ≤ 0.20, the number of Ni atoms entering the Bi2212 lattice increases gradually with increasing x. These Ni atoms preferentially occupy Sr-sites, resulting in a gradual increase in the a and c axis lengths of Bi2212 structure. The formation of containing-Ni Bi2212 lattice is mainly derived from the insertion of sufficient Ni–O two-dimensional (2D) monomers. Contrarily, when x > 0.20, these Ni–O 2D monomers will preferentially form the NiO particle and the chance of Ni atoms entering the Bi2212 lattice is reduced, which leads to a shrinkage of Bi2212 lattice parameters. Besides, under high-pressure (0–20 GPa) condition, Raman spectrum analysis shows that the OSr peak significantly shifts to the higher wavenumber and Bi2212 phase could still maintain the tetragonal structure, suggesting that it has a relatively high structure stability.

High-pressure conformational and crystal polymorphs in 1-hexyl-3-methylimidazolium perfluorobutanesulfonate ionic liquid

An ionic liquid (IL) with conformational polymorphs indicated complicated phase transitions under high pressure (HP). The IL was 1-hexyl-3-methylimidazolium perfluorobutanesulfonate ([C6mim][PFBS]), which has cationic and anionic conformational degrees of freedom. Using HP Raman spectroscopy, a competition between cation and anion conformers corresponded to the HP crystal polymorph. The folding cation appeared at 3.7 GPa due to its flexibility. The rigid [PFBS]− anion also formed the gauche‘ conformer at 7.6 GPa for higher packing efficiency. The conformational flexibility was adjusted depending on pressure. The pressure-variant/invariant conformations were connected with the HP crystal polymorph of [C6mim][PFBS].

Pressure-induced superconductivity in Bi4(I1−x Br x )4 crystals grown by chemical vapor transport and flux methods

Achieving superconductivity in topological materials is thought as a promising route for realizing topological superconductivity, which may provide potential applications to quantum computation. Previously, rich superconducting phases have been reported in the pressurized Bi4I4 and Bi4Br4 crystals which belong to an interesting quasi-one-dimensional topological system. In this work, we have performed a high-pressure study on some Bi4(I1−x Br x )4 crystals grown by two different methods. Remarkably, crystals grown by the chemical vapor transport (CVT) method and the self-flux method show clearly different pressure effects. In the CVT-grown crystals, only one superconducting transition is observed, while three superconducting transitions can be detected in crystals grown by the flux method. Through comparisons of the pressure-dependent phase diagrams and the upper critical field behaviors in the two kinds of crystals, the higher superconducting transition (>6 K) in the flux-grown crystals is suggested to come from the residual Bi. High-pressure Raman spectroscopy measurements on both kinds of crystals have confirmed the occurrence of a similar structural transition around 10 GPa in Br-doped samples. Overall, our data could be helpful for identifying the intrinsic pressure-induced superconductivity in various Bi-based materials.

Quartz-in-garnet (QuiG) under pressure: insights from in situ Raman spectroscopy

Elastic geothermobarometry relies on the contrast between the thermal expansion and compressibility of a mineral inclusion and its surrounding host, leading to a residual pressure in the inclusion (Pinc) that may differ significantly from the external pressure. Quartz-in-garnet (QuiG) inclusion-host systems are widely used in elastic geothermobarometry to estimate the inclusion entrapment conditions and thus the rock petrogenesis. To elucidate the behaviour of QuiG at elevated pressures, we have applied in situ high-pressure Raman spectroscopy on three QuiG samples having Pinc close to 0 GPa at room temperature. We demonstrate that upon pressure increase, the garnet host acts as a shield to the softer quartz inclusion. Consequently, the Pinc increases with a smaller rate compared to that of the external pressure. Up to 2.5 GPa, the evolution of Pinc calculated from the Raman data agrees very well with prediction from the equations of state. Furthermore, the behaviour of a quartz inclusion in a relatively thin host specimen was explored up to external pressures of 7 GPa. Our results indicate that the shielding effect of the host (even if only partial because of the insufficient distance between the inclusion and the host surface) can keep the quartz inclusions thermodynamically stable up to about 2 GPa above the equilibrium quartz–coesite phase boundary. In addition, the partial shielding leads to the development of anisotropic symmetry-breaking stresses and quartz inclusions undergo a reversible crossover to a lower symmetry state. Given that the presence of non-hydrostatic stress may influence the quartz-to-coesite phase boundary, especially at elevated temperatures relevant for entrapment conditions, our results emphasize the importance of elastic anisotropy of QuiG systems, especially when quartz inclusion entrapment occurs under conditions close to the coesite stability field.

Survival of Zirconium-Based Metal-Organic Framework Crystallinity at Extreme Pressures.

Recent research on metal-organic frameworks (MOFs) has shown a shift from considering only the crystalline high-porosity phases to exploring their amorphous counterparts. Applying pressure to a crystalline MOF is a common method of amorphization, as MOFs contain large void spaces that can collapse, reducing the accessible surface area. This can be either a desired change or indeed an unwanted side effect of the application of pressure. In either case, understanding the MOF's pressure response is extremely important. Three such MOFs with varying pore sizes (UiO-66, MOF-808, and NU-1000) were investigated using in situ high-pressure X-ray diffraction and Raman spectroscopy. Partial crystallinity was observed in all three MOFs above 10 GPa, along with some recovery of crystallinity on return to ambient conditions if the frameworks were not compressed above thresholds of 13.3, 14.2, and 12.3 GPa for UiO-66, MOF-808, and NU-1000, respectively. This threshold was marked by an unexpected increase in one or more lattice parameters with pressure in all MOFs. Comparison of compressibility between MOFs suggests penetration of the pressure-transmitting oil into MOF-808 and NU-1000. The survival of some crystallinity above 10 GPa in all of these MOFs despite their differing pore sizes and extents of oil penetration demonstrates the importance of high-pressure characterization of known structures.

Optical-vibration properties and pressure-induced phase transition in (In,Sc)2Ge2O7 pyrogermanates

Thortveitite-type (T-type) scandium and indium pyrogermanates were obtained through a solid-state reaction route. The crystal structures, morphologies, and chemical compositions of these compounds were investigated by X-ray diffraction and transmission electron microscopy techniques. The optical-vibration properties were evaluated by Raman scattering and infrared spectroscopy. Reflectivity far-infrared data were obtained for sintered Sc2Ge2O7 samples, which exhibited good surfaces after polishing, allowing the determination of the infrared optical functions, the complete polar phonon characteristics, the intrinsic dielectric constant and the unloaded quality factor. Because of the poor surface reflectivity of In2Ge2O7 samples, only mid-infrared absorbance data could be collected by using loose powders in an attenuated total reflectance accessory. By using polarized Raman spectroscopy on both ceramic materials, at room temperature and ambient pressure, all the 15 active Raman modes predicted by group theory for the monoclinic C2/m T-type structure were identified and assigned. Further, the phase stabilities of In2Ge2O7 and Sc2Ge2O7 were studied by high-pressure Raman spectroscopy. In the limit of pressures studied here (up to 10 GPa), a reversible structural phase transition (SPT) for In2Ge2O7 and Sc2Ge2O7 was induced by pressures of 4.2 GPa and 2.4 GPa, respectively. These would correspond to the reported C2/m (#12) ↔ P21/c (#14) SPT. Representative Raman spectra of the high-pressure phase for both materials were fitted and 24 first-order Raman modes were depicted for each material, a number greater than compatible with a proposed distorted and oxygen-deficient fluorite-like structure, but explained by an analysis of the gtroup-subgroup constraints of this SPT.

Pressure-Induced Ferroelastic Transition Drives a Large Shape Change in a Ni(II) Complex Single Crystal.

Crystals with significant length reduction at an accessible low pressure are highly desirable for piezo-responsive devices. Here, we show a molecular crystal [Ni(en)3](ox) (en = ethylenediamine and ox = oxalate anion) that exhibits an abrupt shape change with a contraction rate of ∼4.7% along its c axis near the phase transition pressure of ∼0.2 GPa. High-pressure single-crystal X-ray diffraction and Raman spectroscopy measurements reveal that this material undergoes a first-order ferroelastic transition from high-symmetry trigonal P3̅1c to low-symmetry monoclinic P21/n at ∼0.2 GPa. The oxalate anions serve as unique components, and their disorder-order transformation and rotation of 90° through cooperative intermolecular hydrogen bonding triggered unconventional anisotropic microsize contraction under compression, which can be appreciated visually. Such a prominent directional deformation at a low pressure driven by molecular motors of oxalate anions provides insights for the design of novel molecular crystal-based piezo-responsive switches and actuators in deep-sea environments.

Superconductivity emerging from a pressurized van der Waals kagome material Pd3P2S8

Kagome materials have been reported to possess abundant and peculiar physical properties, which provide an excellent platform to explore exotic quantum states. We present a discovery of superconductivity in van der Waals material Pd3P2S8 composed of Pd kagome lattice under pressure. Pd3P2S8 displays superconductivity for those pressures where the semiconducting-like temperature dependence of the resistivity turns into a metallic one. Moreover, it is found that the increased pressure results in a gradual enhancement of superconducting transition temperature, which finally reaches 6.83 K at 79.5 GPa. Combining high-pressure x-ray diffraction, Raman spectroscopy and theoretical calculations, our results demonstrate that the observed superconductivity induced by high pressure in Pd3P2S8 is closely related to the formation of amorphous phase, which results from the structural instability due to the enhanced coupling between interlayer Pd and S atoms upon compression.

Pressure induced isostructural phase transition with volume expansion in DyFeO3 orthoferrite

The orthorhombic O and O′ structure phases of ABO3-type perovskites possess the same symmetry and quite different physical properties. In this work, a pressure induced isostructural O′–O phase transition with volume expansion and less distortion in DyFeO3 orthoferrite was experimentally observed and studied by high-pressure x-ray diffraction and Raman spectroscopy measurements. Up to 35.2 GPa, DyFeO3 crystallizes in an orthorhombic Pbnm symmetry structure. With no change in the symmetry group, distinct O′-phase and O-phase were verified below 13.1 GPa and above 15.1 GPa, respectively. Meanwhile, the lattice becomes less distorted and metrically pseudo-cubic on the high-pressure side. The cell volume expands by a step in the intermediate pressure window accompanied by a decrease in spontaneous strain. It is suggested that FeO6 octahedra are more compressible than DyO12 sites under pressure. This work claimed the physical mechanism underlying phonon dynamics and variation of local structure symmetry of DyFeO3, which can be considered as the basic view for RFeO3 perovskites.

High-Pressure Structural and Thermodynamic Properties of Cerium Orthosilicates (CeSiO4)

Pressure-induced phase transitions from the zircon structure-type (I41/amd) to the scheelite structure type (I41/a) are known for many ternary oxides systems (ABO4). In this work, we present the first high-pressure study on synthetic stetindite (CeSiO4) by a combination of in situ high-pressure synchrotron powder X-ray diffraction up to 36 GPa, implemented with and without dual sided laser heating, and in situ high-pressure Raman spectroscopy up to 43 GPa. Two phase transitions were identified: zircon to a high-pressure low-symmetry (HPLS) phase at 15 GPa and then to a scheelite at 18 GPa. The latter from HPLS scheelite phase was found irreversible; i.e., scheelite is fully quenchable at ambient conditions, as in other zircon-type phases. The bulk moduli (K0) of stetindite, HPLS, and high-pressure scheelite phases were determined, respectively, as 171(5), 105(4), and 221(40) GPa by fitting to a second-order Birch–Murnaghan equation of state. The pressure derivatives of vibrational modes and Grüneisen parameters of the zircon-structured polymorph are similar to those of other orthosilicate minerals. Due to the larger ionic radii of Ce4+, with respect to Zr4+, stetindite was found to possess a softer bulk modulus and undergo the phase transitions at a lower pressure than zircon (ZrSiO4), such observations are consistent with what were found in coffinite (USiO4).

Pressure effect on the magnetism and crystal structure of magnetoelectric metal-organic framework [CH3NH3][Co(HCOO)3

[CH3NH3][Co(HCOO)3] is the first perovskite-like metal-organic framework exhibiting spin-driven magnetoelectric effects. However, the high-pressure tuning effects on the magnetic properties and crystal structure of [CH3NH3][Co(HCOO)3] have not been studied. In this work, alongside ac magnetic susceptibility measurements, we investigate the magnetic transition temperature evolution under high pressure. Upon increasing the pressure from atmospheric pressure to 0.5 GPa, TN (15.2 K) remains almost unchanged. Continuing to compress the sample results in TN gradually decreasing to 14.8 K at 1.5 GPa. This may be due to pressure induced changes in the bond distance and bond angle of the O-C-O superexchange pathway. In addition, by using high pressure powder X-ray diffraction and Raman spectroscopy, we conducted in-depth research on the pressure dependence of the lattice parameters and Raman modes of [CH3NH3][Co(HCOO)3]. The increase in pressure gives rise to a phase transition from the orthorhombic Pnma to a monoclinic phase at approximately 6.13 GPa. Our study indicates that high pressure can profoundly alter the crystal structure and magnetic properties of perovskite type MOF materials, which could inspire new endeavors in exploring novel phenomena in compressed metal-organic frameworks.