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We performed an in-depth investigation and analysis of the effect of temperature on the Raman-active A-modes of bulk kesterite-type Cu2ZnSnS4 within the 300–460 K temperature range. We acquired the individual contributions to each Raman mode, namely, the thermal expansion and anharmonic interactions terms responsible for the Raman shift and broadening with temperature. Our results indicate that the Raman shift with temperature is dominated by the thermal expansion term, whereas the broadening is mainly governed by three-phonon damping processes in this material. Considering relevant results from the literature, it appears that dimensionality is a key factor in regulating the dominant phonon decay mechanism.

High-pressure and high-temperature Raman spectra of synthetic FeCO 3 siderite and Mg 0.76 Fe 0.24 CO 3 magnesite were measured across the spin transition up to nearly 60 GPa and 700 K. In pure siderite the spin transition is sharp and observed between 44 and 46 GPa, with no discernible temperature dependence up to 700 K. The spin transition in Fe-bearing magnesite (“ferromagnesite”) is also sharp and takes place between 45 and 47 GPa at ambient temperature, whereas the transition pressure range broadens significantly at about 600 K (45–52 GPa). Our results suggest that the onset pressure of the spin transition in the siderite–magnesite solid solution series is independent of temperature and composition up to 700 K, whereas the broadening of the spin transition range at higher temperature is driven by the Mg content of the sample. Finally, comparison of the (Mg,Fe)CO 3 and the (Mg,Fe)O systems indicates that the onset pressure of the spin transition is temperature-independent in both cases, which is rationalized in terms of the FeO 6 octahedral compression.

We have examined the effect of temperature and pressure on the Raman-active G-band of graphene nanoplatelets with an average thickness of 4 nm. Measuring the Raman mode frequency and width of the G-band as a function of temperature and pressure allowed us to extract the individual factors contributing to the frequency and width of the G-band, that is, the volumetric (thermal expansion) and anharmonic (phonon–phonon interactions) terms responsible for the Raman shift and the electron–phonon coupling and anharmonic contributions controlling the width/lifetime of the G-band. Considering the available literature, the significant role of the anharmonic effects in understanding the G-band physical processes in carbon-based systems is highlighted.

Using optical absorption and Raman spectroscopic measurements, in conjunction with the first-principles calculations, a pressure-induced high-spin (HS)-to-low-spin (LS) state electronic transition of Fe2+ (M2-octahedral site) was resolved around 76-80GPa in a natural triphylite-lithiophilite sample with chemical composition (LiFe0.7082+Mn0.292PO4)-Li-M1-Fe-M2 (theoretical composition (LiFe0.52+Mn0.5PO4)-Li-M1-Fe-M2). The optical absorption spectra at ambient conditions consist of a broad doublet band with two constituents (1) (similar to 9330cm(-1)) and (2) (similar to 7110cm(-1)), resulting from the electronic spin-allowed transition (T2gEg)-T-5-E-5 of octahedral (HSFe2+)-Fe-M2. Both (1) and (2) bands shift non-linearly with pressure to higher energies up to similar to 55GPa. In the optical absorption spectrum measured at similar to 81GPa, the aforementioned HS-related bands disappear, whereas a new broadband with an intensity maximum close to 16,360cm(-1) appears, superimposed on the tail of the high-energy ligand-to-metal O2-Fe2+ charge-transfer absorption edge. We assign this new band to the electronic spin-allowed dd-transition (1)A(1g)(1)T(1g) of LS Fe2+ in octahedral coordination. The high-pressure Raman spectra evidence the Fe2+ HS-to-LS transition mainly from the abrupt shift of the P-O symmetric stretching modes to lower frequencies at similar to 76GPa, the highest pressure achieved in the Raman spectroscopic experiments. Calculations indicated that the presence of Mn-M2(2+) simply shifts the isostructural HS-to-LS transition to higher pressures compared to the triphylite Fe-M2(2+) end-member, in qualitative agreement with our experimental observations.

We have conducted high pressure far-infrared absorbance and Raman spectroscopic investigations on a natural iron-free dolomite sample up to 40 GPa. Comparison between the present observations and literature results unraveled the effect of hydrostatic conditions on the high pressure dolomite polymorph adopted close to 40 GPa, i.e. the triclinic Dol-IIIc modification. In particular, non-hydrostatic conditions impose structural disorder at these pressures, whereas hydrostatic conditions allow the detection of an ordered Dol-IIIc vibrational response. Hence, hydrostatic conditions appear to be a key ingredient for modeling carbon subduction at lower mantle conditions. Our complementary first-principles calculations verified the far-infrared vibrational response of the ambient- and high pressure dolomite phases.

Our joint high-pressure and high-temperature mid-infrared absorbance and Raman investigations on a synthetic strontianite sample led to the construction of the respective pressure–temperature P–T phase diagram (maximum P = 38 GPa, maximum T = 800 K). Our results allowed for the determination of the P–T slope for the onset pressure of the aragonite Pmcn → post-aragonite Pmmn structural transition reported in the literature, which is found to be negative and equal to ΔP/ΔT = − 0.012 GPa/K. The determined SrCO3 P–T phase diagram appears consistent with the respective P–T phase diagrams of relevant aragonite-type carbonates. In addition, we provide the first ever measured far-infrared absorbance spectra under pressure for the family of aragonite-type carbonates. Our complementary first-principle calculations were able to reproduce the infrared spectra of both Pmcn and Pmmn phases of strontianite.

A combined high-pressure mid-infrared absorption and Raman spectroscopy study on a natural CaMg0.98Fe0.02(CO3)2 dolomite sample was performed both at ambient and high temperatures. A pressure–temperature phase diagram was constructed for all the reported dolomite ambient- and high-pressure polymorphs. In addition, a local distortion of the ambient-pressure dolomite structure was identified close to 11 GPa, just before the transition toward the first known high-pressure phase. All the Clausius–Clapeyron slopes are found to be positive with similar magnitudes. Complementary first-principles calculations suggest a metastable nature of the high-pressure dolomite polymorphs. Finally, theoretical spectroscopy is used to interpret and discuss the observed changes in the measured vibrational spectra.

Applied physics letters 110(4), 041905 (2017). doi:10.1063/1.4974941, We have investigated the high-pressure structural and vibrational behavior of the ordered kesterite-type Cu$_{2}$ZnSnS$_{4}$ compound. Our investigations have revealed two structural transitions: a kesterite-to-disordered kesterite transition was observed between 7 and 9 GPa, which involves a Zn/Cu disorder within the respective cationic sublattice, whereas a rocksalt-type structure was realized at ∼15 GPa. The latter transition is accompanied by a cationic coordination increase from fourfold-to-sixfold with respect to the sulfur anions. The predicted kesterite-to-stannite transition was not detected. Furthermore, our high-pressure Raman studies have shown that the aforementioned Zn/Cu cationic disorder will always be present in Cu$_{2}$ZnSnS$_{4}$ under relatively moderate compression., Published by AIP Publishing , Melville, NY

The series of Cr-chalcogenide spinels ACr2X4 (A = Zn, Cd, Hg; X = S, Se) exhibits a rich phase diagram upon compression, as revealed by our recent investigations. There exist, however, some open questions regarding the role of cations in the observed structural transitions. In order to address these queries, we have performed X-ray diffraction and Raman spectroscopic studies on the ZnCr2S4 spinel up to 42 GPa, chosen mainly due to the similarity of the Zn2+ and Cr3+ cationic radii. Two reversible structural transitions were identified at 22 and 33 GPa, into a I41/amd and an orthorhombic phase, respectively. Close comparison with the behavior of relevant Cr-spinels revealed that the structural transitions are mainly governed by the competition of the magnetic exchange interactions present in these systems, and not by steric effects. In addition, careful inspection of the starting Fd3m phase revealed a previously unnoticed isostructural transition. The latter is intimately related to changes in the electro...

Τhe magnetoelectric $\mathrm{ZnC}{\mathrm{r}}_{2}\mathrm{S}{\mathrm{e}}_{4}$ spinel, with space group $Fd\overline{3}m$, undergoes a reversible first-order structural transition initiating at 17 GPa, as revealed by our high-pressure x-ray diffraction studies at room temperature. We tentatively assign the high-pressure modification to an $A\mathrm{M}{\mathrm{o}}_{2}{\mathrm{S}}_{4}$-type phase, a distorted variant of the monoclinic $\mathrm{C}{\mathrm{r}}_{3}{\mathrm{S}}_{4}$ structure. Furthermore, our Raman investigation provides evidence for a pressure-induced insulator-metal transition. Our density functional theory calculations successfully reproduce the structural transition. They indicate significant band gap and magnetic moment reduction accompanying the pressure-induced structural modification. We discuss our findings in conjunction with the available high-pressure results on other Cr-based chalcogenide spinels.

High-pressure Raman spectroscopy and x-ray diffraction of Sb2S3 up to 53 GPa reveals two phase transitions at 5 GPa and 15 GPa. The first transition is evidenced by noticeable compressibility changes in distinct Raman-active modes, in the lattice parameter axial ratios, the unit cell volume, as well as in specific interatomic bond lengths and bond angles. By taking into account relevant results from the literature, we assign these effects to a second-order isostructural transition arising from an electronic topological transition in Sb2S3 near 5 GPa. Close comparison between Sb2S3 and Sb2Se3 up to 10 GPa reveals a slightly diverse structural behavior for these two compounds after the isostructural transition pressure. This structural diversity appears to account for the different pressure-induced electronic behavior of Sb2S3 and Sb2Se3 up to 10 GPa, i.e. the absence of an insulator-metal transition in Sb2S3 up to that pressure. Finally, the second high-pressure modification appearing above 15 GPa appears to trigger a structural disorder at ~20 GPa; full decompression from 53 GPa leads to the recovery of an amorphous state.

The high-pressure structural and vibrational properties of Bi2S3 have been probed up to 65 GPa with a combination of experimental and theoretical methods. The ambient-pressure Pnma structure is found to persist up to 50 GPa; further compression leads to structural disorder. Closer inspection of our structural and Raman spectroscopic results reveals notable compressibility changes in specific structural parameters of the Pnma phase beyond 4-6 GPa. By taking the available literature into account, we speculate that a second-order isostructural transition is realized near that pressure, originating probably from a topological modification of the Bi2S3 electronic structure near that pressure. Finally, the Bi(3+) lone-electron pair (LEP) stereochemical activity decreases against pressure increase; an utter vanishing, however, is not expected until 1 Mbar. This persistence of the Bi(3+) LEP activity in Bi2S3 can explain the absence of any structural transitions toward higher crystalline symmetries in the investigated pressure range.

The cubic HgCr2Se4 spinel undergoes two structural transitions upon pressure increase. Initially, the ambient-pressure Fd-3m phase transforms into a tetragonal I41/amd structure above 15 GPa. We speculate that this Fd-3m-I41/amd transition is accompanied by an insulator-to-metal transition, resulting in the vanishing of the Raman signal after the structural transformation. Further compression of HgCr2Se4 leads to structural disorder beyond 21 GPa. Our spin-resolved band structure calculations reveal significant changes in the electronic structure of HgCr2Se4 after the Fd-3m-I41/amd transition, whereas the ferromagnetic interactions are found to dominate in both structures.

Selected members of the A2B3 (A = Sb, Bi; B = Se, Te) family are topological insulators. The Sb2Se3 compound does not exhibit any topological properties at ambient conditions; a recent high-pressure study, however, indicated that pressure transforms Sb2Se3 from a band insulator into a topological insulator above ~2 GPa; in addition, three structural transitions were proposed to occur up to 25 GPa. Partly motivated by these results, we have performed x-ray diffraction and Raman spectroscopy investigations on Sb2Se3 under pressure up to 65 GPa. We have identified only one reversible structural transition: the initial Pnma structure transforms into a disordered cubic bcc alloy above 51 GPa. On the other hand, our high-pressure Raman study did not reproduce the previous results; we attribute the discrepancies to the effects of the different pressure transmitting media used in the high-pressure experiments. We discuss the structural behavior of Sb2Se3 within the A2B3 (A = Sb, Bi; B = Se, Te) series.