High-pressure Raman Spectroscopy Research Articles

Destabilizing excitonic insulator phase by pressure tuning of exciton-phonon coupling

The authors use high-pressure Raman spectroscopy along with a first-principles model analysis to study the role of exciton-phonon coupling in stabilizing the excitonic insulator phase of Ta${}_{2}$NiSe${}_{5}$ at room temperature.

Lattice dynamics of the topological Dirac semimetal LaAgSb2 with charge density wave ordering

LaAgSb$_{2}$ is a rare material, which offers the opportunity to investigate the complex interplay between charge density wave (CDW) ordering and topology protected electronic band structure. As both of these phenomena are governed by the structural symmetries, a comprehensive study of the lattice dynamics is highly desirable. In this report, we present the results of temperature and pressure dependent Raman spectroscopy and x-ray diffraction in single crystalline LaAgSb$_{2}$. Our results confirm that Raman spectroscopy is a highly sensitive tool to probe CDW ordering phenomenon, particularly the low-temperature second CDW transition in LaAgSb$_{2}$, which appears as a very weak anomaly in most experiments. The crystal orientation-dependent measurements provide the evolution of Raman modes with crystallographic symmetries and can be further studied through group symmetry analysis. The low-temperature x-ray diffraction data show the emergence of structural modulations corresponding to the CDW instability. The combined high-pressure Raman spectroscopy and synchrotron x-ray diffraction reveal multiple structural phase transitions through lowering of crystalline symmetries, which are also expected to lead to electronic topological transitions.

High-Pressure Raman Study of Fe(IO3)3: Soft-Mode Behavior Driven by Coordination Changes of Iodine Atoms

We report high-pressure Raman spectroscopy studies of Fe(IO3)3 up to nearly 21 GPa that have been interpreted with the help of density-functional theory calculations, that include the calculation of phonon dispersion curves and elastic constants at different pressures. Zero-pressure Raman-active mode frequencies and their pressure dependences have been determined. Modes have been assigned and correlated to atomic movements with the help of calculations. Interestingly, in the high-frequency region there are several modes that soften under compression. These modes have been identified as internal vibrations of the IO3 coordination polyhedron. Their unusual behavior is a consequence of the changes induced by pressure in the coordination sphere of iodine, which gradually change from a three-fold to almost six-fold coordination under compression. The coordination change is favored by the decrease of the stereoactivity of the iodine lone electron pair, so that likely real six-fold coordination is attained after a first-order phase transition previously reported to occur above 21 GPa. The strong non-linear behavior found in Raman-active modes as well as in theoretically calculated elastic constants has been discovered to be related to the occurrence of two previously unreported isostructural phase transitions at 1.5-2.0 GPa and 5.7-6.0 GPa as shown by dynamic instabilities close to the Brillouin zone center.

Low-temperature and high-pressure Raman spectroscopy of 2-hydroxy-3,4,6-trimethoxyacetophenone isolated from the Croton anisodontus Müll.Arg.

The acetophenone 2-hydroxy-3,4,6-trimethoxyacetophene (C11O5H14, hereafter named as HTMCX) was obtained from the stem bark of Croton anisodontus Müll.Arg., an endemic species found in the caatinga of Northeast Brazil. The HTMCX crystal was investigated via Raman spectroscopy as a function of the temperature and pressure, in the intervals ranging from 300 to 8 K and from ambient pressure up to 9.7 GPa, respectively. In low-temperature experiments, we observed changes in the slope of the wavenumber versus temperature curves in the spectral range of 30–350 cm−1 at ∼ 210 K, as well as discontinuities in the wavenumber of modes in the region for wavenumbers higher than 1300 cm−1. These modifications are compatible with a conformational change occurring at around 210 K. Regarding the high-pressure experiments, we found that the wavenumber for modes located in the low-wavenumber region (ω < 300 cm-1) does not show any significant modification, indicating that the atmospheric pressure structure is stable up to 9.7 GPa. Minor changes evidenced the occurrence of conformational changes, which should be associated with an effect related to a slight distortion of the crystal unit cell but preserving its symmetry. The changes observed in certain spectral regions also evidenced the occurrence of conformational changes in the range from 2.0 to 4.0 GPa and 5.0 to 7.2 GPa.

Silicate Bond Characteristics in Calcium–Silicate–Hydrates Determined by High Pressure Raman Spectroscopy

The mechanical and thermal properties of the gigatonnes of concrete produced annually are strongly affected by the anharmonicity of the chemical bonds in its main binding phase, nanocrystalline cal...

High-pressure Raman study of the alkaline-earth metal fulleride, Ca2.75C60

The structural stability and electronic properties of [Formula: see text] are probed by means of high-pressure Raman spectroscopy using two different pressure transmitting media that lead to practically identical results. Although [Formula: see text] is isostructural with the rare-earth metal fulleride, [Formula: see text] of the same stoichiometry, the pressure coefficients of characteristic intramolecular [Formula: see text] modes are larger than those in the [Formula: see text] counterpart but similar to those in the pristine [Formula: see text] solid. Since the reduced pressure coefficients in the Sm fulleride have been attributed to strong [Formula: see text] coupling, our findings for the isostructural Ca fulleride are compatible with a reduced orbital mixing and [Formula: see text] coupling.

Understanding the Mechanism of Ferroelectric Phase Transition in RbHSO4: A High-Pressure Raman Investigation.

Previous high-pressure dielectric and diffraction studies on rubidium hydrogen sulfate (RbHSO4) observed ferroelectric phase transition below 1 GPa pressure. We have performed high-pressure Raman spectroscopy studies on RbHSO4 up to a maximum pressure of 5.15 GPa and at ambient temperature to understand the microscopic origin and mechanism of ferroelectric transition. On the basis of the pressure dependence of Raman mode frequencies and their full-width at half-maxima, we observed a transition around a pressure of 0.3 GPa, similar to the ferroelectric transition discovered in dielectric measurements, followed by another transition around 2.4 GPa. These phase transitions are evident from the appearance/disappearance of Raman-active modes and the change in the slope of frequencies with pressures. From the pressure dependence of the S-O and S-OH frequencies, we deduce that HSO4- ion ordering results in ferroelectric phase transition around 0.3 GPa. Further, the transition around 2.4 GPa pressure is associated with significant changes in the stretching and bending vibrational frequencies and indicates a structural phase transition with possible lowering of the crystal symmetry. Interestingly, no significant changes are observed in the Raman spectrum around 1 GPa, at which a phase transition was noticed in earlier X-ray and dielectric studies.

Pressure-Induced Dimerization of C60 at Room Temperature as Revealed by an In Situ Spectroscopy Study Using an Infrared Laser

Using in situ high-pressure Raman spectroscopy and X-ray diffraction, the polymerization and structure evaluation of C60 were studied up to 16 GPa at room temperature. The use of an 830 nm laser successfully eliminated the photo-polymerization of C60, which has interfered with the pressure effect in previous studies when a laser with a shorter wavelength was used as excitation. It was found that face-centered cubic (fcc) structured C60 transformed into simple cubic (sc) C60 due to the hint of free rotation for the C60 at 0.3 GPa. The pressure-induced dimerization of C60 was found to occur at about 3.2 GPa at room temperature. Our results suggest the benefit and importance of the choice of the infrared laser as the excitation laser.

Unconventional high-pressure Raman spectroscopy study of kinetic and peak pressure effects in plagioclase feldspars

We present the results of a high-pressure semi-hydrostatic study of two plagioclase minerals, andesine and albite, using diamond anvil cells (DACs) to characterize in situ variations in Raman spectra under different static pressures. In this work, we also examined the kinetic effects on deformation at both long and short timescales through non-traditional experiments in which the DAC was either dropped or struck with a mallet. We examined the effects of strain rate, quench rate, and pressure duration on the Raman spectra of plagioclase. We observed that amorphization occurred in all the plagioclase samples we analyzed, and that amorphization onset and permanence differ depending on the composition, kinetics, energy input, and peak pressure. In andesine, samples pressurized above a peak pressure of 18 GPa, amorphization is permanent. Below this critical pressure, the phase has ‘memory’, and crystalline andesine reforms on decompression. Our findings suggest the presence of a thermodynamic energy well in andesine around 18 GPa, and we show that any additional energy input while close to 18 GPa results in amorphization becoming permanent. The effect of the energy well may be relevant for longer duration impacts. For such impacts, equilibrium state studies of deformation and phase formation were previously considered to be applicable. These experiments illuminating the presence of memory effects in plagioclase have implications for comparing static compression, in which samples are measured while under compression, with shock compression, for which samples are measured after decompression.

Study on the High-Pressure Behavior of Goethite up to 32 GPa Using X-Ray Diffraction, Raman, and Electrical Impedance Spectroscopy

Goethite is a major iron-bearing sedimentary mineral on Earth. In this study, we conducted in situ high-pressure x-ray diffraction, Raman, and electrical impedance spectroscopy measurements of goethite using a diamond anvil cell (DAC) at room temperature and high pressures up to 32 GPa. We observed feature changes in both the Raman spectra and electrical resistance at about 5 and 11 GPa. However, the x-ray diffraction patterns show no structural phase transition in the entire pressure range of the study. The derived pressure-volume (P-V) data show a smooth compression curve with no clear evidence of any second-order phase transition. Fitting the volumetric data to the second-order Birch–Murnaghan equation of state yields V0 = 138.9 ± 0.5 Å3 and K0 = 126 ± 5 GPa.

Pressure-modulated lattice structural evolution in multilayer ZrS3

Recently, ZrS3, a group IV transition—metal trichalcogenides has attracted much attention due to its light—emission properties. Pressure engineering can effectively modify the photoelectric properties of crystals by tuning their atomic displacement. However, pressure-induced phase transitions in multilayer ZrS3 have not been fully elucidated. This work investigated the lattice structural evolution in compressed multilayer ZrS3 through high-pressure Raman spectroscopy and first-principle calculations. The lattice distorted at 2.5 GPa, as evidenced by a split of Raman mode I. Further compression led to a phase transition at 10.8 GPa, which was related to the rearrangement of dangling S–S pairs along the a-axis. Our study provides a foundation for exploring the potential of pseudo-1D material systems for applications such as electrical and thermal transport, and luminous performance.

Anomalous lattice compression in the hexagonal La2O3– A high pressure X-ray diffraction, Raman spectroscopy and first principle study

High pressure behavior of hexagonal rare earth sesquioxide La2O3 have been investigated using X-ray diffraction, Raman spectroscopy and first principle calculations. Though the hexagonal structure is stable up to 26.5 GPa, incompressibility along the a axis is visible above 9.7 GPa. Rietveld structure refinements in conjunction with the Stephans anisotropic strain broadening model revealed the onset of an atypical bond compression and modification in the relative intensities of the diffraction peaks at ∼5.6 GPa. A significant increase in the intensity of 100 reflection and a clear reduction in the intensity of 103 reflection above 5.6 GPa suggests that pressure induces sliding of the adjacent La–O layers in opposite directions rather than compressing along the a axis. Further, a negative correlation of in-plane strain with pressure above 5.6 GPa indicate the layer sliding is accompanied by a reduction of in-plane strain in the hexagonal structure. Raman studies show the lifting of the degeneracy of the two stretching modes, in-plane Eg and out of plane A1g, and the change of slope of ω vs. P curve for the two in-plane Eg modes at 3.6 GPa. First principle density functional theory calculation substantiates our experimental observations that the pressure induced anisotropic strain distribution is driving the system into low energy configurations. The Birch –Murnaghan equation of state fit to the experimental pressure-volume data yielded a bulk modulus value of B0 = 102(5) GPa with B′0 = 9.8(1.0) for P ≤ 9.7 GPa, in good agreement with the 114 GPa of density functional theory calculations.

In situ high pressure neutron diffraction and Raman spectroscopy of 20BaO-80TeO2 glass.

The short-range structure of 20BaO–80TeO2 glass was studied in situ by high pressure neutron diffraction and high pressure Raman spectroscopy. Neutron diffraction measurements were performed at the PEARL instrument of the ISIS spallation neutron source up to a maximum pressure of 9.0 ± 0.5 GPa. The diffraction data was analysed via reverse Monte Carlo simulations and the changes in the glass short-range structural properties, Ba–O, Te–O and O–O bond lengths and speciation were studied as a function of pressure. Te–O co-ordination increases from 3.51 ± 0.05 to 3.73 ± 0.05, Ba–O coordination from 6.24 ± 0.19 to 6.99 ± 0.34 and O–O coordination from 6.00 ± 0.05 to 6.69 ± 0.06 with an increase in pressure from ambient to 9.0 GPa. In situ high pressure Raman studies found that the ratio of intensities of the two bands at 668 cm−1 and 724 cm−1 increases from 0.99 to 1.18 on applying pressure up to 19.28 ± 0.01 GPa, and that these changes are due to the conversion of TeO3 into TeO4 structural units in the tellurite network. It is found that pressure causes densification of the tellurite network by the enhancement of co-ordination of cations, and an increase in distribution of Te–O and Ba–O bond lengths. The original glass structure is restored upon the release of pressure.

Size and morphology effects on the high pressure behaviors of Mn3O4 nanorods.

The high-pressure behaviors of Mn3O4 nanorods were studied by high pressure powder synchrotron X-ray diffraction and Raman spectroscopy. We found that the initial hausmannite phase transforms into the orthorhombic CaTi2O4-type structure, and then to the marokite-like phase upon compression. Upon decompression, the marokite-like phase is retained at the ambient pressure. Compared with Mn3O4 bulk and nanoparticles, Mn3O4 nanorods show obviously different phase transition behaviors. Upon compression, the phase transition sequence of Mn3O4 nanorods is similar with the nanoparticles, while the decompression behavior is consistent with the bulk counterparts. The hausmannite phase shows higher stability and smaller bulk modulus in Mn3O4 nanorods than those of the corresponding bulk and nanoparticles. We proposed that the higher phase stability and compressibility of the nanorods are concerned with their nanosize effects and the rod morphology. Both the growth orientation and the suppressed Jahn–Teller distortion of the Mn3O4 nanorods are crucial factors for their high pressure behaviors.

High pressure exploration in the Li-Ln-V-O system.

Using in situ high pressure Raman spectroscopy, two structural changes were observed in a sample of the composition LiLa5O5(VO4)2. Taking this into account and by combining different conditions, three new compounds were further obtained from high pressure-high temperature synthesis. Their crystal structure description was done using the antiphase approach, which implies the presence of oxygen-centered [OLn4] building units, where Ln is La for (1) β-LiLa5O5(VO4)2 and (2) β-LiLa2O2(VO4) or Nd for (3) LiNd5O5(VO4)2 compounds. (1) crystallizes in the triclinic space group P1[combining macron] with unit cell parameters of a = 5.8167(15) Å, b = 12.2954(28) Å, c = 18.7221(69) Å, α = 102.03(2)°, β = 98.76(2)°, and γ = 103.54(2)°; a 3D structure was deduced from the ambient pressure polymorph. (2) also crystallizes in P1[combining macron] with a = 5.8144(7) Å, b = 5.8167(7) Å, c = 8.5272(1) Å, α = 98.184(7)°, β = 100.662(7)° and γ = 92.579(7)°. It shows a 2D structure with [La2O2]2+ layers surrounded by [LiO4] and [VO4] tetrahedra sharing corners and edges. (3) exhibits a 3D architecture isotypic with AP-LiLa5O5(VO4)2. The crucial role of high pressure in such types of synthesis and materials is also discussed.

Experimental evidence of crystal symmetry protection for the topological nodal line semimetal state in ZrSiS

Tunable symmetry breaking plays a crucial role for the manipulation of topological phases of quantum matter. Here, through combined high-pressure magneto-transport measurements, Raman spectroscopy, and X-ray diffraction, we demonstrate a pressure-induced topological phase transition in nodal-line semimetal ZrSiS. Symmetry analysis and first-principles calculations suggest that this pressure-induced topological phase transition may be attributed to weak lattice distortions by non-hydrostatic compression, which breaks some crystal symmetries, such as the mirror and inversion symmetries. This finding provides some experimental evidence for crystal symmetry protection for the topological semimetal state, which is at the heart of topological relativistic fermion physics.

Stability, composition, and crystal structure of Fe-bearing Phase E in the transition zone

Abstract Fe-bearing phase E coexisting with ringwoodite and wadsleyite has been synthesized at near-geotherm temperatures in hydrous KLB-1 peridotite compositions held at 18 and 19 GPa, and 1400 °C for 27 h. The long heating duration time of syntheses implies that phase E can be a stable component of the mantle under hydrous conditions. Single-crystal X-ray diffraction analyses show that the M1 octahedral site is 72.1–75.2 at% occupied, whereas the M2 and tetrahedral Si sites are 2.4–2.9 at% and 18.9–19.8 at% occupied, respectively. The M1 site occupancies show a positive correlation with Fe/Mg molar ratios, indicating that Fe mainly occupies the M1 site in the phase E structure. High-pressure Raman spectroscopy shows that the framework Raman frequencies of Fe-bearing phase E increase continuously with increasing pressures up to 19 GPa at room temperature, and there is no indication for a major change in the crystal structure. If transition-zone regions adjacent to subducting slabs are hydrated by fluids generated at the top of the lower mantle, Fe-bearing phase E is expected to occur at wadsleyite-ringwoodite phase transition boundary (about 520 km) as an important phase for incorporating water.

Structural Phase Transition and Metallization of Nanocrystalline Rutile Investigated by High-Pressure Raman Spectroscopy and Electrical Conductivity

We investigate the structural, vibrational, and electrical transport properties of nanocrystalline rutile and its high-pressure polymorphs by Raman spectroscopy, and AC complex impedance spectroscopy in conjunction with the high-resolution transmission electron microscopy (HRTEM) up to ~25.0 GPa using the diamond anvil cell (DAC). Experimental results indicate that the structural phase transition and metallization for nanocrystalline rutile occurred with increasing pressure up to ~12.3 and ~14.5 GPa, respectively. The structural phase transition of sample at ~12.3 GPa is confirmed as a baddeleyite phase, which is verified by six new Raman characteristic peaks. The metallization of the baddeleyite phase is manifested by the temperature-dependent electrical conductivity measurements at ~14.5 GPa. However, upon decompression, the structural phase transition from the metallic baddeleyite to columbite phases at ~7.2 GPa is characterized by the inflexion point of the pressure coefficient and the pressure-dependent electrical conductivity. The recovered columbite phase is always retained to the atmospheric condition, which belongs to an irreversible phase transformation.

Raman study of pressure-induced dissociative transitions in nitrogen

The pressure-induced intermolecular and intramolecular dissociation transitions in nitrogen have been investigated in this work. The experimental intermolecular dissociative transition pressures for solid molecular phases (β, δ, δloc, ε, ζ, ζ’, κ and η) have been carefully determined up to 136 GPa by high-pressure Raman spectroscopy, and the high-frequency Raman vibrons of molecular solids has been assigned by analyzing the local molecular polarization properties. We demonstrate that pressure-induced symmetry breaking leads to a series of solid molecular phases in nitrogen associated with a splitting of vibrons. The polymeric cg-N was synthesized at about 134 GPa and above 2000 K, and the pressure dependence of Raman mode for cg-N was studied in conditions of increasing pressure up to 172 GPa and decreasing pressure down to 46 GPa. The zero-pressure mode-Grüneisen parameter of the cg-N Raman A mode was also extrapolated to be 1.24 ± 0.02.

Crystal structure of norsethite-type BaMn(CO3)2 and its pressure-induced transition investigated by Raman spectroscopy

Single crystals of norsethite-type carbonate BaMn(CO3)2 up to 200 μm in size were synthesized in a closed cavity under high pressure–temperature (P–T) conditions. Electron microprobe analyses revealed the composition of 49.00–49.09 wt% BaO and 22.66–22.74 wt% MnO, which correspond well to the ideal formula of Ba1.0Mn1.0(CO3)2. Accurate crystalline structural data were determined from single crystal X-ray diffraction (XRD). The $$R\overline{3} c$$ space-group with a doubled c-axis and $$R\overline{3} m$$ space-group were used to refine the crystal structure of BaMn(CO3)2. It is proved that $$R\overline{3} m$$ is the most probable space-group for the BaMn(CO3)2 crystal structure because no superstructure reflections were observed in the X-ray images. The unit cell parameters were identified to be a = 5.0827(2) A and c = 17.2797(10) A in the rhombohedral symmetry of the $$R\overline{3} m$$ space-group with a final R-value of 0.0184. High-pressure Raman spectroscopy was performed up to 10 GPa at room temperature, and Raman band shifts ( $$\frac{{{\text{d}}\nu_{i} }}{{{\text{d}}P}}$$ ) were quantified. Each Raman vibration underwent resolvable splitting and the corresponding $$\frac{{{\text{d}}\nu_{i} }}{{{\text{d}}P}}$$ showed a pronounced jump as the pressure reached 3.8 GPa arising from a pressure-induced transition.