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We have studied the dielectric, structural, and vibrational properties of 0.95NaNbO3–0.05(Na0.50Bi0.50)TiO3 (05NBT) solid solution belonging to the NN–NBT family that possess efficient power functionality and large electro-strain. We found that the magnitude of dielectric permittivity increases with temperature and shows diffuse peak anomalies at various temperatures. Detailed analyses of temperature-dependent neutron diffraction patterns revealed that the sample has the ideal cubic perovskite structure above 650 °C. On cooling, it undergoes a series of structural phase transitions from cubic to orthorhombic phases due to condensation of various lattice instabilities. The amplitude of antiferrodistortive distortion mode analysis showed that the value of primary distortive mode decreases on heating and, finally, diminishes at the phase transition temperatures. The displacement patterns corresponding to various lattice instabilities responsible for this structural phase transition are identified. Raman spectra exhibit noticeable changes in the relative intensities between the peaks as well as broadening, merging, and disappearance of certain peaks on heating. The symmetrical and asymmetrical stretching modes (ν1 and ν2) of BO6 octahedra exhibit opposite behavior with temperature while the bending modes merge into a single broad band. This provides clear evidence of local structural changes in the system. [ABSTRACT FROM AUTHOR]

We have conducted a detailed high-pressure (HP) investigation on Eu-doped BaTiO3 using angle-resolved x-ray diffraction, Raman spectroscopy, and dielectric permittivity measurements. The x-ray diffraction data analysis shows a pressure-induced structural phase transition from the ambient tetragonal to the mixed cubic and tetragonal phases above 1.4 GPa. The tetragonality of the sample due to the internal deformation of the TiO6 octahedra caused by the charge difference from Eu doping cannot be lifted by pressure. Softening, weakening, and disappearance of low-frequency Raman modes indicate ferroelectric tetragonal to the paraelectric cubic phase transition. However, the pressure-induced increase in the intensity of [E(LO), A1(LO)] and the octahedral breathing modes indicate that the local structural inhomogeneity remains in the crystal and is responsible for spontaneous polarization in the sample. The low-frequency electronic scattering response suggests pressure-induced carrier delocalization, leading to a semi-metallic state in the system. Our HP dielectric constant data can be explained by the presence of pressure-induced localized clusters of microscopic ferroelectric ordering. Our results suggest that the HP phase coexistence leads to a ferroelectric-like semi-metallic state in Eu-doped BaTiO3 under extreme quantum limits. [ABSTRACT FROM AUTHOR]

We have conducted a detailed high-pressure (HP) investigation on Eu-doped BaTiO3 using angle-resolved x-ray diffraction, Raman spectroscopy, and dielectric permittivity measurements. The x-ray diffraction data analysis shows a pressure-induced structural phase transition from the ambient tetragonal to the mixed cubic and tetragonal phases above 1.4 GPa. The tetragonality of the sample due to the internal deformation of the TiO6 octahedra caused by the charge difference from Eu doping cannot be lifted by pressure. Softening, weakening, and disappearance of low-frequency Raman modes indicate ferroelectric tetragonal to the paraelectric cubic phase transition. However, the pressure-induced increase in the intensity of [E(LO), A1(LO)] and the octahedral breathing modes indicate that the local structural inhomogeneity remains in the crystal and is responsible for spontaneous polarization in the sample. The low-frequency electronic scattering response suggests pressure-induced carrier delocalization, leading to a semi-metallic state in the system. Our HP dielectric constant data can be explained by the presence of pressure-induced localized clusters of microscopic ferroelectric ordering. Our results suggest that the HP phase coexistence leads to a ferroelectric-like semi-metallic state in Eu-doped BaTiO3 under extreme quantum limits. [ABSTRACT FROM AUTHOR]

We here present the normal dynamics technique, which recasts the Newton's equations of motion in terms of phonon normal modes by exploiting a proper sampling of the reciprocal space. After introducing the theoretical background, we discuss how the reciprocal space sampling enables us to (i) obtain a computational speedup by selecting which and how many wave vectors of the Brillouin zone will be considered and (ii) account for distortions realized across large atomic distances without the use of large simulation cells. We implemented the approach into an open-source code, which we used to present three case studies: in the first one, we elucidate the general strategy for the sampling of the reciprocal space; in the second one, we illustrate the potential of the approach by studying the stabilization effect of temperature in α-uranium; and in the last one, we investigate the characterization of Raman spectra at different temperatures in MoS2/MX2 transition metal dichalcogenide heterostructures. Finally, we discuss how the procedure is general and can be used to simulate periodic, semiperiodic, and finite systems such as crystals, slabs, nanoclusters, or molecules. [ABSTRACT FROM AUTHOR]

Organic–inorganic hybrid perovskite quantum wells exhibit electronic structures with properties intermediate between those of inorganic semiconductors and molecular crystals. In these systems, periodic layers of organic spacer molecules occupy the interstitial spaces between perovskite sheets, thereby confining electronic excitations to two dimensions. Here, we investigate spectroscopic line broadening mechanisms for phonons coupled to excitons in lead-iodide layered perovskites with phenyl ethyl ammonium (PEA) and azobenzene ethyl ammonium (AzoEA) spacer cations. Using a modified Elliot line shape analysis for the absorbance and photoluminescence spectra, polaron binding energies of 11.2 and 17.5 meV are calculated for (PEA)2PbI4 and (AzoEA)2PbI4, respectively. To determine whether the polaron stabilization processes influence the dephasing mechanisms of coupled phonons, five-pulse coherent Raman spectroscopies are applied to the two systems under electronically resonant conditions. The prominence of inhomogeneous line broadening mechanisms detected in (AzoEA)2PbI4 suggests that thermal fluctuations involving the deformable organic phase broaden the distributions of phonon frequencies within the quantum wells. In addition, our data indicate that polaron stabilization primarily involves photoinduced reorganization of the organic phases for both systems, whereas the impulsively excited phonons represent less than 10% of the total polaron binding energy. The signal generation mechanisms associated with our fifth-order coherent Raman experiments are explored with a perturbative model in which cumulant expansions are used to account for time-coincident vibrational dephasing and polaron stabilization processes. [ABSTRACT FROM AUTHOR]

Calculation of Raman scattering from molecular dynamics (MD) simulations requires accurate modeling of the evolution of the electronic polarizability of the system along its MD trajectory. For large systems, this necessitates the use of atomistic models to represent the dependence of electronic polarizability on atomic coordinates. The bond polarizability model (BPM) is the simplest such model and has been used for modeling the Raman spectra of molecular systems but has not been applied to solid-state systems. Here, we systematically investigate the accuracy and limitations of the BPM parameterized from the density functional theory results for a series of simple molecules, such as CO2, SO2, H2S, H2O, NH3, and CH4; the more complex CH2O, CH3OH, CH3CH2OH, and thiophene molecules; and the BaTiO3 and CsPbBr3 perovskite solids. We find that BPM can reliably reproduce the overall features of the Raman spectra, such as shifts of peak positions. However, with the exception of highly symmetric systems, the assumption of non-interacting bonds limits the quantitative accuracy of the BPM; this assumption also leads to qualitatively inaccurate polarizability evolution and Raman spectra for systems where large deviations from the ground state structure are present. [ABSTRACT FROM AUTHOR]

Monolayer indium selenide (InSe), a two-dimensional material, exhibits exceptional electronic and optical properties that can be significantly modulated via strain engineering. This study employed density functional theory to examine the structural and vibrational properties of monolayer InSe under varying biaxial strains. Phonon dispersion analysis confirmed the stability of monolayer InSe, as indicated by the absence of imaginary frequencies. The study extensively detailed how Raman and infrared spectra adjust under strain, showing shifts in peak positions and variations in intensity that reflect changes in lattice symmetry and electronic structures. Specific findings include the stiffening of the A′1 mode and the increased intensity of E″ and E′ modes under strain, suggesting enhanced polarizability and asymmetric vibrations. Moreover, the Raman intensity for the E′ mode at 167.3 cm−1 increased under both tensile and compressive strain due to enhanced polarizability and symmetry disruption, while the IR intensity for the A″2 mode at 192.1 cm−1 decreased, likely from diminished dipole moment changes. In contrast, the low-frequency modes, such as E″ at 36.8 cm−1, demonstrated insensitivity to strain, implying a minimal impact on heavier atoms within these modes. Overall, this study highlights the sensitivity of vibrational modes to strain-induced changes, providing valuable insights into the behavior of monolayer InSe under mechanical stress. [ABSTRACT FROM AUTHOR]

Temperature is an important parameter to be monitored in new wearable electronic devices. Layered black phosphorus (BP) has inherent good thermal stability and semiconductor properties and has a promising application as a temperature sensing layer. Here, we investigate the temperature sensing properties of BP, using in situ Raman spectroscopy and x-ray diffraction techniques. Flexible sensors are constructed, and temperature response is investigated in the range of 6–38 °C. The prospect application for monitoring the temperature of human body parts is demonstrated. The results show that the BP-based temperature sensors demonstrate good negative temperature coefficient characteristics and display high sensitivity and reproducible sensing performance. The temperature-dependent performance suggests the feasibility of BP as a sensitive layer in a wide temperature range. This work paves the way for exploring new applications of amazing layered materials, such as BP, in wearable electronic devices. [ABSTRACT FROM AUTHOR]

The laser power mediated changes in the Raman line shape have been considered in terms of interference between discrete phonon states ρ and the electronic continuum states ϰ contributed by Urbach tail states. The laser-induced effects are treated in terms of the increase in the surface temperature and thereby the scaling of electronic disorder, i.e., Urbach energy, which can further contribute to the electron–phonon interactions. Therefore, the visualization of this effect is attempted analytically as a perturbation term in the Hamiltonian, which clearly accounts for the observed changes with laser power. This has been investigated based on the experimental results of laser power dependent Raman spectra of bulk EuFeO3 and silicon nanowires, which are found to provide convincing interpretations. [ABSTRACT FROM AUTHOR]

Two-dimensional or other thin materials have high potential for use in next-generation electronic and optoelectronic devices. Recently, tellurium has gained much interest due to its broad applicability prospects. In this work, the physical properties of thin tellurium layers fabricated using two relatively simple and inexpensive technologies based on the deposition from a chemical solution and by thermal evaporation were compared. The morphology of the grown surfaces was analyzed using atomic force microscopy. The chemically deposited tellurium surface consists of nanometer-sized flakes, while polycrystalline layers are formed in the case of deposition by thermal evaporation. Additionally, the characteristics of the fabricated samples varied depending on their thickness, as observed in both Raman spectroscopy and THz spectroscopy measurements. Furthermore, the non-contact optical pump THz probe technique revealed that the layers had different carrier lifetimes and mobilities. The carrier lifetime of samples deposited by thermal evaporation is short, less than 40 ps, with mobility up to a few hundred cm2/V s. In contrast, chemically deposited samples have a longer carrier lifetime, ranging more than 500 ps, and superior mobility up to 1000 cm2/V s. [ABSTRACT FROM AUTHOR]

Traditionally, the stuffing model has been used to describe stress generation in chemically strengthened glass. Nevertheless, the associated unrealistic conditions, including an imaginary volume expansion and its suppression in an adiabatic closed system, inhibit a thorough understanding of the process. In this study, we propose a thermodynamic model in an isothermal open system to enable ion exchange without an imaginary volume expansion. We derive a fundamental equation and verify it using atomistic images obtained by Raman spectroscopy and nuclear magnetic resonance. This study paves the way for further atomistic design and development of strengthened glasses. [ABSTRACT FROM AUTHOR]

Using resonant Raman spectroscopy with 632.8 nm (1.96 eV) laser, we describe the Raman spectra of single crystals of transition metal dichalcogenides with nominal composition MoSe(2−x)Sx for x = 0.2. Changes in Raman spectra at some regions of the sample indicated non-stoichiometry and, in particular, chalcogenide vacancies. At low temperatures around 77 K, we observed unusual temperature dependent enhancement in the intensity of non-zone center modes as well as overtones and combination modes in Raman spectra. This enhancement in the intensity is correlated to the resonance achieved in the non-stoichiometric regions of the crystal at low temperatures. Observed resonance is attributed to modification in the electronic structure due to defects. Energy dispersive x-ray spectroscopy measurements confirmed chalcogenide vacancies in the crystals. The change in the electronic structure due to defects is also corroborated by photoluminescence spectroscopy measurements. [ABSTRACT FROM AUTHOR]

Standing striations with a unique pattern have been observed in a radio-frequency-generated hydrogen plasma. The striation pattern consists of a sequence of closely spaced bright ring doublets and two types of dark gaps of different widths. The bright and dark regions in striations were spectroscopically resolved with the Balmer series and the Fulcher band emission lines of hydrogen. Temperatures in these fine structures were determined. In general, the wider dark gap has a higher excitation temperature than the nearby narrower ones in the striation pattern sequence. Bright regions are rotationally hotter than the adjacent dark ones. However, for vibrational temperatures, the trends are not so obvious. No clear pressure dependence of temperatures was observed in striations within the pressure range of maintaining stable standing striations in this work. In addition to optical emission spectroscopy, we used graphite granules as in situ probes for plasma conditions in different striation regions. The striated hydrogen plasma-treated graphite granules were analyzed with Raman spectroscopy. The observed hydrogen-graphite interaction was correlated with the measured temperatures and the fine structures of striations in a discharge tube. [ABSTRACT FROM AUTHOR]

Ethane ( C 2 H 6 ) is anticipated to be the most stable compound within the carbon–hydrogen system under the 100 GPa pressure range. Nevertheless, the properties of ethane under pressure are still poorly documented. Here, we present a comprehensive study of the structural and vibrational properties of C 2 H 6 in a diamond anvil cell at pressures up to 150 GPa. To obtain detailed data, ethane single-crystal was grown in a helium pressure-transmitting medium. Utilizing single-crystal x-ray diffraction, the distortion mechanism between the tetragonal and monoclinic phases, occurring over the 3.2–5.2 GPa pressure range, is disclosed. Subsequently, no phase transition is observed up to 150 GPa. The accurately measured compression curve is compared to various computational approximations. The vibrational modes measured by Raman spectroscopy and infrared absorption are well identified, and their evolution is well reproduced by ab initio calculations. In particular, an unusual anticrossing phenomenon occurs near 40 GPa between a rocking and a stretching mode, likely attributable to intermolecular interactions through hydrogen bonding. [ABSTRACT FROM AUTHOR]

We implanted Fe+ ions in nanodiamond (ND) powder containing negatively charged nitrogen-vacancy (NV−) centers and studied their Raman spectra and optically detected magnetic resonance (ODMR) in various applied magnetic fields with green light (532 nm) excitation. In Raman spectra, we observed a blue shift of the NV− peak associated with the conversion of the electronic sp3 configuration to the disordered sp2 one typical for the carbon/graphite structure. In the ODMR spectra, we observed a red shift of the resonance position caused by local heating by an absorptive environment that recovers after annealing. To reveal the red shift mechanism in ODMR, we created a controlled absorptive environment around ND by adding iron-based Fe2O3 and graphitic sp2 powders to the ND suspension. This admixture caused a substantial increase in the observed shift proportional to the applied laser power, corresponding to an increase in the local temperature by 150–180 K. This surprisingly large shift is absent in non-irradiated NV-ND powders, is associated only with the modification of the local temperature by the absorptive environment of NV-NDs, and can be studied using ODMR signals of NV−. [ABSTRACT FROM AUTHOR]

The singlet fission process involves the conversion of one singlet excited state into two triplet states, which has significant potential for enhancing the energy utilization efficiency of solar cells. Carotenoid, a typical π conjugated chromophore, exhibits specific aggregate morphologies known to display singlet fission behavior. In this study, we investigate the singlet fission process in lycopene H-aggregates using femtosecond stimulated Raman spectroscopy aided by quantum chemical calculation. The experimental results reveal two reaction pathways that effectively relax the S2 (11Bu+) state populations in lycopene H-aggregates: a monomer-like singlet excited state relaxation pathway through S2 (11Bu+) → 11Bu− → S1 (21Ag−) and a dominant sequential singlet fission reaction pathway involving the S2 (11Bu+) state, followed by S* state, a triplet pair state [1(TT)], eventually leading to a long lifetime triplet state T1. Importantly, the presence of both anionic and cationic fingerprint Raman peaks in the S* state is indicative of a substantial charge-transfer character. [ABSTRACT FROM AUTHOR]

In the present study, we have investigated the effect of magnetic Cr doping on the transport properties of a sputtered Bi2Se3 thin film on the SrTiO3 (110) substrate. The high-resolution x-ray diffraction and Raman spectroscopy measurements revealed the growth of rhombohedral Bi2Se3 thin films. Further electronic and compositional analysis was done by x-ray photoemission spectroscopy and Rutherford backscattering spectroscopy, and the x-value was estimated to be 0.18 in the Bi2−xCrxSe3 thin film. The variation in the resistivity with temperature (2–300 K) revealed the metallic nature in undoped Bi2Se3 up to 30 K and upturn resistivity below 30 K. The Cr-doped Bi2Se3 resistivity data show a traditional semiconducting nature up to 25 K and take an abrupt upturn resistivity below 25 K. The resistivity behavior of both samples was explained by adopting a model that consists of the total resistance, a combination of bulk and surface resistance in parallel. The bulk bandgap value determined by this method is obtained to be 256 meV in an undoped Bi2Se3 thin film. Magnetoconductance data of the undoped thin film revealed a weak anti-localization (WAL) effect, while the Cr-doped thin film showed a weak localization (WL) effect at low temperatures (<50 K). At low magnetic field and low temperature, a competing nature of WAL and WL effects was prominent in the Cr-doped film. A drastic increase in the electrical resistance suggests that Cr doping can significantly modify the electrical properties of Bi2Se3 thin films, which could have potential applications in futuristic devices. [ABSTRACT FROM AUTHOR]

The integration of Au nanorods in tip-enhanced Raman spectroscopy (TERS) presents a significant increase in the enhancement factor, primarily due to the gap-mode effect. By aligning Au nanorods in parallel, we construct an Au nanorod lattice, referred to as the Au nanolattice, which further amplifies the advantages of TERS imaging due to the induced inter-nanorod surface plasmon resonance. A critical aspect in this research involves investigating the distribution of hotspots within the nanolattice during TERS measurements. Additionally, we demonstrate that the tip–lattice nanocavity is a predominant factor in determining both the intensity and spatial distribution of these hotspots. Employing the experimental and simulation results, we illustrate the enhancement effect of the tip–lattice cavity and elucidate the connection between the hotspot intensity and cavity size. This comprehensive approach contributes to our understanding of the nano-lattice's role in TERS and offers valuable insights for optimizing nanophotonic applications. [ABSTRACT FROM AUTHOR]

The effect of carbon coating on a surface structure of a high-dose implanted/annealed silicon carbide (SiC) during annealing was examined using scanning probe microscopy (SPM), deep-ultraviolet (DUV) Raman spectroscopy, and transmission electron microscopy (TEM). In SPM, the surfaces of 500- and 30 °C-implanted/annealed SiC samples without coating exhibited a periodic-step structure and granular structure, respectively. The difference between these surfaces is attributed to the absence or presence of residual implantation damage. In contrast, surface flatness was maintained in the 500 °C-implanted/annealed SiC sample with carbon coating. However, the surface of the coated 30 °C-implanted/annealed SiC sample exhibited a geometric structure with a lattice pattern parallel to the ⟨ 11 2 ¯ 0 ⟩ axes. The DUV Raman spectra and TEM images indicated that the implanted layer of this sample metamorphosed into a mixture of 3C-SiC twin domains and amorphous-SiC regions. During the cooling process after annealing, the 3C-SiC region was more raised than the amorphous-SiC region owing to the difference in the thermal expansion coefficients, thus resulting in the generation of a geometric surface structure. In the metamorphosed implanted layer, the carbon coating does not completely prevent surface roughening. [ABSTRACT FROM AUTHOR]

Cooperativity is essential for the proper functioning of numerous proteins by allosteric interactions. Hemoglobin from Scapharca inaequivalvis (HbI) is a homodimeric protein that can serve as a minimal unit for studying cooperativity. We investigated the structural changes in HbI after carbon monoxide dissociation using time-resolved resonance Raman spectroscopy and observed structural rearrangements in the Fe–proximal histidine bond, the position of the heme in the pocket, and the hydrogen bonds between heme and interfacial water upon ligand dissociation. Some of the spectral changes were different from those observed for human adult hemoglobin due to differences in subunit assembly and quaternary changes. The structural rearrangements were similar for the singly and doubly dissociated species but occurred at different rates. The rates of the observed rearrangements indicated that they occurred synchronously with subunit rotation and are influenced by intersubunit coupling, which underlies the positive cooperativity of HbI. [ABSTRACT FROM AUTHOR]

The rotational relaxation behavior of D2(1,12) in a D2–N2 mixture was investigated using coherent anti-Stokes Raman scattering (CARS) technique. The rovibrational level v = 1 and J = 12 of D2 was selectively excited through stimulated Raman pumping while monitoring the temporal evolution of population for D2(1, J ≤ 12) molecules using time-resolved CARS spectroscopy. The results demonstrate that the rotational relaxation processes of D2(1,12) encompass both multi-quantum relaxation and continuous single-quantum relaxation. When α, the molar ratio of N2, is less than 0.5, D2(1,12) predominantly undergoes a single quantum relaxation process transition. However, when α ≥ 0.5, the multi-quantum relaxation mechanism gradually predominates. The total rotational relaxation rate coefficients of D2(1,12) collisions with N2 and D2 at 295 K were determined to be 3.974 × 10−14 and 1.179 × 10−14 cm3 s−1, respectively. The temperature dependence of rotational relaxation rate of D2(1,12) was investigated within the temperature range of 295–453 K. With increasing temperature, the dominant relaxation process exhibited an accelerated behavior, while the minor relaxation process remained largely unaffected. The rotational temperature of the D2 molecule at various N2 molar ratios was determined through the utilization of Boltzmann plots. The rotational temperature undergoes a rapid decline within 2 μs, corresponding to the near-resonant rotation–vibration relaxation process of D2(1,12) collisions with N2. The system reaches a quasi-equilibrium state when the delay time is 3 μs. The findings of this study can serve as a valuable empirical basis for further validation of the kinetic theory and simulation. [ABSTRACT FROM AUTHOR]

The rotational relaxation behavior of D2(1,12) in a D2–N2 mixture was investigated using coherent anti-Stokes Raman scattering (CARS) technique. The rovibrational level v = 1 and J = 12 of D2 was selectively excited through stimulated Raman pumping while monitoring the temporal evolution of population for D2(1, J ≤ 12) molecules using time-resolved CARS spectroscopy. The results demonstrate that the rotational relaxation processes of D2(1,12) encompass both multi-quantum relaxation and continuous single-quantum relaxation. When α, the molar ratio of N2, is less than 0.5, D2(1,12) predominantly undergoes a single quantum relaxation process transition. However, when α ≥ 0.5, the multi-quantum relaxation mechanism gradually predominates. The total rotational relaxation rate coefficients of D2(1,12) collisions with N2 and D2 at 295 K were determined to be 3.974 × 10−14 and 1.179 × 10−14 cm3 s−1, respectively. The temperature dependence of rotational relaxation rate of D2(1,12) was investigated within the temperature range of 295–453 K. With increasing temperature, the dominant relaxation process exhibited an accelerated behavior, while the minor relaxation process remained largely unaffected. The rotational temperature of the D2 molecule at various N2 molar ratios was determined through the utilization of Boltzmann plots. The rotational temperature undergoes a rapid decline within 2 μs, corresponding to the near-resonant rotation–vibration relaxation process of D2(1,12) collisions with N2. The system reaches a quasi-equilibrium state when the delay time is 3 μs. The findings of this study can serve as a valuable empirical basis for further validation of the kinetic theory and simulation. [ABSTRACT FROM AUTHOR]

Understanding the structural behavior of solid hydrogen under high pressures is crucial for uncovering its unique properties and potential applications. In this study, starting from the phase I of solid hydrogen—free-rotator hcp structure, we conduct extensive ab initio molecular dynamics calculations to simulate the cooling, heating, and equilibrium processes within a pressure range of 80–260 GPa. Without relying on any structure previously predicted, we identify the high-pressure phase structures of solid hydrogen as P21/c for phase II, P6522 for phase III, and BG1BG2BG3 six-layer structure for phase IV, which are different from those proposed previously using the structure-search method. The reasonability of these structures are validated by Raman spectra and x-ray diffraction patterns by comparison with the experimental results. Our results actually show pronounced changes in the c/a ratio between phases I, III, and IV, which hold no brief for the experimental interpretation of an isostructural hcp transformations for phases I–III–IV. [ABSTRACT FROM AUTHOR]

Objectives: The objective was to evaluate the polymerization efficiency of different bulk-fill resin-based composites cured by monowave and polywave light-curing units, by assessment of the degree of conversion and Vickers microhardness at different depths. Method and materials: Two commercially available bulk-fill resin-based composites were used: Filtek One Bulk Fill Restorative (3M ESPE) and Tetric N-Ceram Bulk Fill (Ivoclar Vivadent). The light-curing units utilized were two LED light-curing units: a monowave LED light-curing unit (BlueLEX LD-105, Monitex) and a polywave LED light-curing unit (Twin Wave GT-2000, Monitex). For each test, 20 cylindrical specimens (4 mm diameter, 4 mm thickness) were prepared from each bulk-fill resin-based composite using a split Teflon mold. Ten specimens were light-cured by the monowave light-curing unit and the other ten were light-cured by the polywave light-curing unit according to the manufacturer's recommendations. Attenuated total reflectance-Fourier transform infrared spectroscopy (ATRFTIR) was used to assess the degree of conversion, and a Vickers microhardness tester was used to assess Vickers microhardness. Statistical analysis was performed using three-way ANOVA and Tukey post-hoc tests (P < .05). Results: The degree of conversion and Vickers microhardness in bulk-fill resin-based composites containing only camphorquinone as photoinitiator were similar when cured with either monowave or polywave light-curing units. However, bulk-fill resin-based composites containing a combination of photoinitiators exhibited significantly higher degree of conversion and Vickers microhardness when cured with a polywave light-curing unit. Although all groups showed statistically significant differences between the top and bottom surfaces regarding degree of conversion and Vickers microhardness, all of them showed bottom/top ratios > 80% regarding degree of conversion and Vickers microhardness. Conclusion: The polywave light-curing unit enhanced the polymerization efficiency of bulk-fill resin-based composites especially when the latter contained a combination of photoinitiators, but does not prevent the use of a monowave light-curing unit. [ABSTRACT FROM AUTHOR]

Redox control of glasses is paramount both to their fusion process and to obtaining the desired properties of high technological glasses. However, the link between melting parameters, such as temperature, furnace atmosphere, or quenching rate, and the redox state of the final products is poorly understood. In this work, in situ x-ray absorption near-edge structure (XANES) data at Ce L3-edge data were acquired at high temperatures on cerium-containing sodium aluminosilicate glasses, allowing the determination of thermodynamic constants necessary to predict the cerium redox state over a wide temperature range (900–1500 °C). The results obtained were compared to the Raman spectra of samples quenched at different temperatures. Our findings demonstrate that the quench performed was fast enough to block the cerium oxidation state, meaning the redox measured at room temperature is representative of a high temperature state. This was further verified by room temperature Raman spectroscopy, where a relationship was found between the spectra and melting conditions. Wet chemical analysis, XANES at Ce L3-edge, Raman spectroscopy, and optical absorption spectroscopy were successfully used to determine the redox state of cerium in aluminosilicates. [ABSTRACT FROM AUTHOR]

In view of the current situation in which the OD-stretch vibrational spectra have been scarcely computed with non-polarizable rigid D2O models, we investigate the IR and Raman spectra of D2O by using a newly-reported model TIP4P/2005-HW. From the comparison between the calculations and experimental data, we find the excellent performance of TIP4P/2005-HW for vibrational spectroscopy of D2O in the same manner as TIP4P/2005 for H2O, although one may still conveniently employ an alternative method that regards OH as putative OD to calculate the OD-stretch spectra with similar quality from TIP4P/2005 trajectories. We also demonstrate that the appropriate setting for the spectral simulation of D2O under the time-averaging approximation reflects the slower dynamics (i.e., slower motion of translation and rotation due to the heavier mass and stronger hydrogen bond) of D2O than H2O. Moreover, we show from the theoretical calculations that the established interpretation of the OH-stretch spectra of H2O is finely applicable to the OD-stretch of D2O. [ABSTRACT FROM AUTHOR]

Choline dihydrogen phosphate, [Chol][H2PO4], is a proton-conducting ionic plastic crystal exhibiting a complicated sequence of phase transitions. Here, we address the argument in the literature around the thermal properties of [Chol][H2PO4] using Raman and infrared microspectroscopy. The known structure of the low-temperature crystal, which contains the anti-conformer of [Chol]+ and hydrogen-bonded dimers of anions, was used to do periodic density functional theory calculations of the vibrational frequencies. Raman spectra indicate that the solid–solid transition at 20 °C is linked to a conformational change to the gauche [Chol] conformer with a concurrent local rearrangement of the anions. The distinct bands of lattice modes in the low-frequency range of the Raman spectra vanish at the 20 °C transition. Given the ease with which metastable crystals can be produced, Raman mappings demonstrate that a sample of [Chol][H2PO4] at ambient temperature can contain a combination of anti- and gauche conformers. Heating to 120 °C causes continuous changes in the local environment of anions rather than melting as suggested by a recent calorimetric investigation of [Chol][H2PO4]. The monotonic change in vibrational spectra is consistent with earlier observations of a very small entropy of fusion and no abrupt jump in the temperature dependence of ionic conductivity along the phase transitions of [Chol][H2PO4]. [ABSTRACT FROM AUTHOR]

This study leverages two-pulse femtosecond stimulated Raman spectroscopy (2FSRS) to characterize molecular systems with avoided crossings (ACs) and conical intersections (CIs) in their low-lying excited electronic states. By simulating 2FSRS spectra of microscopically inspired ACs and CIs models, we demonstrate that 2FSRS not only delivers valuable information on the molecular parameters characterizing ACs and CIs but also helps distinguish between these two systems. [ABSTRACT FROM AUTHOR]

Two-dimensional terahertz–infrared–visible (2D TIRV) spectroscopy directly measures the coupling between quantum high-frequency vibrations and classical low-frequency modes of molecular motion. In addition to coupling strength, the signal intensity in 2D TIRV spectroscopy can also depend on the selection rules of the excited transitions. Here, we explore the selection rules in 2D TIRV spectroscopy by studying the coupling between the high-frequency CH3 stretching and low-frequency vibrations of liquid dimethyl sulfoxide (DMSO). Different excitation pathways are addressed using variations in laser pulse timing and different polarizations of exciting pulses and detected signals. The DMSO signals generated via different excitation pathways can be readily distinguished in the spectrum. The intensities of different excitation pathways vary unequally with changes in polarization. We explain how this difference stems from the intensities of polarized and depolarized Raman and hyper-Raman spectra of high-frequency modes. These results apply to various systems and will help design and interpret new 2D TIRV spectroscopy experiments. [ABSTRACT FROM AUTHOR]

To elucidate the atomistic origin of volume relaxation in soda-lime silicate glass annealed below the glass transition temperature (Tg), the experimental and calculated Raman spectra were compared. By decomposing the calculated Raman spectra into specific groups of atoms, the Raman peaks at 800, 950, 1050, 1100, and 1150 cm−1 were attributed to oxygen and silicon in Si–O–Si, non-bridging oxygen in the Q2 unit, bridging oxygen in low-angle Si–O–Si, non-bridging oxygen in the Q4 unit, and bridging oxygen in high-angle Si–O–Si, respectively. Based on these attributions, we found that by decreasing the fictive temperature by annealing below Tg − 70 K, a homogenization reaction Q2 + Q4 → 2Q3 and an increase in average Si–O–Si angle occurred simultaneously. By molecular dynamics simulation, we clarified how the experimentally demonstrated increase in average Si–O–Si angle contributes to volume shrinkage; increasing Si–O–Si angles can expand the space inside the rings, and Na can be inserted into the ring center. [ABSTRACT FROM AUTHOR]

Lithium niobate ( LiNbO 3 , LN) on insulator (LNOI) has emerged as a promising platform for integrated photonics, due to the strong optical confinement and excellent nonlinear optical and electrical characteristics of LN crystal. Focused ion beam (FIB) as a versatile technique has become a typical way to fabricate LNOI microstructures. However, due to the bombardment of Ga + ions during fabrication, the LN lattice is damaged, which would deteriorate the performance of LNOI devices. Thus, the recognition of the damage formed by FIB fabrication is necessary for the control and optimization of the properties of LN microstructures. However, previous studies on this issue have not delved into it from a lattice perspective. Here, we conducted an investigation into the damage inflicted on LN film due to FIB fabrication and the subsequent impact of buffered oxide etching (BOE) treatment on this damage using Raman spectroscopy. Our findings indicate that the interaction between Ga + ions and LN film results in lattice amorphization, as well as a reduction in the ionic bonding and lattice stress within LN. Furthermore, absorption spectra were acquired both before and after BOE treatment, revealing the emergence of additional optical losses attributed to Ga + ions. Notably, these defects responsible for optical losses are predominantly concentrated near the surface of the milled LN film, and BOE treatment proves efficient in their removal. This study contributes to further understanding of the defect structure in LN film after FIB fabrication, as well as repairing the damage and, thus, improving the performance of LN microstructures. [ABSTRACT FROM AUTHOR]

Radiation damage in semiconductor materials is a crucial concern for electronic applications, especially in the fields of space, military, nuclear, and medical electronics. With the advancements in semiconductor fabrication techniques and the trend of miniaturization, the quality of semiconductor materials and their susceptibility to radiation-induced defects have become more important than ever. In this context, machine learning (ML) algorithms have emerged as a promising tool to study minor radiation-induced defects in semiconductor materials. In this study, we propose a sensitive non-destructive technique for investigating radiation-induced defects using multivariate statistical analyses combined with Raman spectroscopy. Raman spectroscopy is a contactless and non-destructive method widely used to characterize semiconductor materials and their defects. The multivariate statistical methods applied in analyzing the Raman spectra provide high sensitivity in detecting minor radiation-induced defects. The proposed technique was demonstrated by categorizing 100–500 kGy irradiated GaAs wafers into samples with low and high irradiation levels using linear discrimination analysis ML algorithms. Despite the high similarity in the obtained Raman spectra, the ML algorithms correctly predicted the blind testing samples, highlighting the effectiveness of ML in defect study. This study provides a promising approach for detecting minor radiation-induced defects in semiconductor materials and can be extended to other semiconductor materials and devices. [ABSTRACT FROM AUTHOR]

Temperature-dependent Raman spectral studies of BiFeO3 (BFO) films coated on three different substrates, viz., conducting Si (BFO-Si), sapphire (BFO-SAP), and fluorine-doped tin oxide (BFO-FTO), are reported between 123 and 773 K. The activity of Bi–O and Fe–O modes in these samples as a function of temperature shows different spectral features despite having synthesized from the same precursor. To understand the source of these variations, the spectra obtained on the above films were compared with those of bulk BiFeO3 (BFO-bulk) prepared via spark-plasma sintering. As the temperature increases, modes corresponding to the Bi–O activity at low frequency (120–180 cm−1) exhibit a redshift in their positions in all the samples. Between 350 and 550 K, BFO-SAP and BFO-Si samples show discernible anomalies in the positions of modes corresponding to the Fe–O activity (200–500 cm−1), which is not observed in the BFO-bulk and BFO-FTO samples. These anomalies are more pronounced for the modes between 350 and 500 cm−1, suggesting alterations in the Néel transition temperature (∼643 K for BiFeO3). Concurrently, another composite film of BiFeO3–CoFe2O4 coated on the Si substrate is explored. Raman studies on the composite film are used to compare and verify the influence of the substrate and defects on the magnetic ordering as a function of temperature. Our study highlights the significance and relevance of using Raman spectroscopy as a tool to discern various factors leading to local structural and magnetic variation in a given compound. [ABSTRACT FROM AUTHOR]

Surface-enhanced Raman spectroscopy (SERS) is a powerful tool for elucidating the molecular makeup of materials. It possesses the unique characteristics of single-molecule sensitivity and extremely high specificity. However, the true potential of SERS, particularly in capturing the biochemical content of particles, remains underexplored. In this study, we harnessed transformer neural networks to interpret SERS spectra, aiming to discern the amino acid profiles within proteins. By training the network on the SERS profiles of 20 amino acids of human proteins, we explore the feasibility of predicting the predominant proteins within the µL-scale detection volume of SERS. Our results highlight a consistent alignment between the models predictions and the proteins known amino acid compositions, deepening our understanding of the inherent information contained within SERS spectra. For instance, the model achieved low root mean square error (RMSE) scores and minimal deviation in the prediction of amino acid compositions for proteins such as Bovine Serum Albumin (BSA), ACE2 protein, and CD63 antigen. This novel methodology offers a robust avenue not only for protein analytics but also sets a precedent for the broader realm of spectral analyses across diverse material categories. It represents a solid step forward to establishing SERS-based proteomics.

The discovery of graphene led to a burst in search for 2D materials originating from layered atomic crystals coupled by van der Waals force. While bulk bismuth crystals share this layered crystal structure, unlike other group V members of the periodic table, its interlayer bonds are stronger such that traditional mechanical cleavage and exfoliation techniques have shown to be inefficient. In this work, we present a novel mechanical cleavage method for exfoliating bismuth by utilizing the stress concentration effect induced by micro-trench SiO 2 structures. As a result, the exfoliated bismuth flakes can achieve thicknesses down to the sub-10 nm range, which are analyzed by atomic force microscopy and Raman spectroscopy. [ABSTRACT FROM AUTHOR]

Tetrahedrite, Cu12Sb4S13, an eco-friendly thermoelectric material with earth-abundant and low-cost constituents, has garnered global interest. This study investigated the thermoelectric characteristics of Ag-added tetrahedrites, which were prepared through solid-state synthesis and subsequently hot-pressed. The minimal temperature dependence of the transport coefficient indicated the presence of strong electron–phonon coupling in the samples. It was observed that Ag addition in tetrahedrite could successfully scatter acoustic phonons, reducing the lattice thermal conductivity while minimally affecting the power factor. The enhanced anharmonicity induced by Ag addition is the primary cause of reduced lattice thermal conductivity. Raman spectroscopy data showed that Ag addition could weaken the Sb–S bond, further supporting the previous argument. Consequently, the lattice thermal conductivity was lowered to ∼0.27 W m−1 K−1 and obtained for the composition Ag0.025 added Cu11.975Sb4S13. A relatively high power factor of ∼1.3 mW m−1 K−2 was obtained for the same composition. Owing to the lowest total thermal conductivity ∼1.09 W m−1 K−1, the sample with composition Ag0.025 added Cu11.975Sb4S13 showed the highest thermoelectric figure of merit of 0.87 at 738 K. [ABSTRACT FROM AUTHOR]

We present structural models for three different amyloid fibril polymorphs prepared from amylin20–29 (sequence SNNFGAILSS) and amyloid-β25–35 (Aβ25–35) (sequence GSNKGAIIGLM) peptides. These models are based on the amide C=O bond and Ramachandran ψ-dihedral angle data from Raman spectroscopy, which were used as structural constraints to guide molecular dynamics (MD) simulations. The resulting structural models indicate that the basic structural motif of amylin20–29 and Aβ25–35 fibrils is extended β-strands. Our data indicate that amylin20–29 forms both antiparallel and parallel β-sheet fibril polymorphs, while Aβ25–35 forms a parallel β-sheet fibril structure. Overall, our work lays the foundation for using Raman spectroscopy in conjunction with MD simulations to determine detailed molecular-level structural models of amyloid fibrils in a manner that complements gold-standard techniques, such as solid-state nuclear magnetic resonance and cryogenic electron microscopy. [ABSTRACT FROM AUTHOR]

Two-dimensional ferroic materials exhibit a variety of functional properties that can be tuned by temperature and pressure. CuInP2S6 is a layered material that is ferrielectric at room temperature and whose properties are a result of the unique structural arrangement of ordered Cu+ and In3+ cations within a (P2S6)4− anion backbone. Here, we investigate the effect of hydrostatic pressure on the structure of CuInP2S6 single crystals through a detailed Raman spectroscopy study. Analysis of the peak frequencies, intensities, and widths reveals four high pressure regimes. At 5 GPa, the material undergoes a monoclinic-trigonal phase transition. At higher pressures (5–12 GPa), we see Raman peak sharpening, indicative of a change in the electronic structure, followed by an incommensurate phase between 12 and 17 GPa. Above 17 GPa, we see evidence for bandgap reduction in material. The original state of the material is fully recovered upon decompression, showing that hydrostatic pressure could be used to tune the electronic and ferrielectric properties of CuInP2S6. [ABSTRACT FROM AUTHOR]

Two-dimensional ferroic materials exhibit a variety of functional properties that can be tuned by temperature and pressure. CuInP2S6 is a layered material that is ferrielectric at room temperature and whose properties are a result of the unique structural arrangement of ordered Cu+ and In3+ cations within a (P2S6)4− anion backbone. Here, we investigate the effect of hydrostatic pressure on the structure of CuInP2S6 single crystals through a detailed Raman spectroscopy study. Analysis of the peak frequencies, intensities, and widths reveals four high pressure regimes. At 5 GPa, the material undergoes a monoclinic-trigonal phase transition. At higher pressures (5–12 GPa), we see Raman peak sharpening, indicative of a change in the electronic structure, followed by an incommensurate phase between 12 and 17 GPa. Above 17 GPa, we see evidence for bandgap reduction in material. The original state of the material is fully recovered upon decompression, showing that hydrostatic pressure could be used to tune the electronic and ferrielectric properties of CuInP2S6. [ABSTRACT FROM AUTHOR]

Prolonging the lifetime of photoinduced hot carriers in lead–halide perovskite quantum dots (QDs) is highly desirable because it can help improve the photovoltaic conversion efficiency. Ligand engineering has recently become a promising strategy to achieve this; nevertheless, mechanistic studies in this field remain limited. Herein, we propose a new scenario of ligand engineering featuring Pb2+/Br− site-selective capping on the surface of CsPbBr3 QDs. Through joint observations of temperature-dependent photoluminescence, ultrafast transient absorption, and Raman spectroscopy of the two contrasting model systems of CsPbBr3 QDs (i.e., capping with organic ligand only vs hybrid organic/inorganic ligands), we reveal that the phononic regulation of Pb–Br stretching at the Br-site (relative to Pb-site) leads to a larger suppression of charge–phonon coupling due to a stronger polaronic screening effect, thereby more effectively retarding the hot-carrier cooling process. This work opens a new route for the manipulation of hot-carrier cooling dynamics in perovskite systems via site-selective ligand engineering. [ABSTRACT FROM AUTHOR]

Silicene, a 2D hexagonal structure of silicon, has shown great promise for next-generation advanced electronic devices due to recent progress. However, one major obstacle to its application and integration into devices is its strong tendency of rapid oxidation in an ambient environment. Enhancing the chemical inertness by means of chemical modification without comprising its unique structure and properties is vital. Here, we report the fabrication of hydrogenated silicene grown on polycrystalline Ag films by means of plasma-enhanced chemical-vapor deposition (PECVD) with proper hydrogen dilution. Our Raman spectroscopy and x-ray diffraction results show the existence of typical monolayer and few-layer silicene. The x-ray photoelectron spectroscopy demonstrates its oxidation resistance after a few minutes of air exposure in a class 100 clean room. We propose that PECVD silicene can be an alternative to molecular-beam-epitaxy silicene for potential low-cost and large-area silicene applications. [ABSTRACT FROM AUTHOR]

GeSnC alloys offer a route to direct bandgap semiconductors for CMOS-compatible lasers, but the use of CBr4 as a carbon source was shown to reduce Sn incorporation by 83%–92%. We report on the role of thermally cracked H in increasing Sn incorporation by 6x–9.5x, restoring up to 71% of the lost Sn, and attribute this increase to removal of Br from the growth surface as HBr prior to formation of volatile groups such as SnBr4. Furthermore, as the H flux is increased, Rutherford backscattering spectroscopy reveals a monotonic increase in both Sn and carbon incorporation. X-ray diffraction reveals tensile-strained films that are pseudomorphic with the substrate. Raman spectroscopy suggests substitutional C incorporation; both x-ray photoelectron spectroscopy and Raman suggest a lack of graphitic carbon or its other phases. For the lowest growth temperatures, scanning transmission electron microscopy reveals nanovoids that may account for the low Sn substitutional fraction in those layers. Conversely, the sample grown at high temperatures displayed abrupt interfaces, notably devoid of any voids, tin, or carbon-rich clusters. Finally, the surface roughness decreases with increasing growth temperature. These results show that atomic hydrogen provides a highly promising route to increase both Sn and C to achieve a strongly direct bandgap for optical gain and active silicon photonics. [ABSTRACT FROM AUTHOR]

Direct bandgap group IV materials could provide intimate integration of lasers, amplifiers, and compact modulators within complementary metal–oxide–semiconductor for smaller, active silicon photonics. Dilute germanium carbides (GeC) with ∼1 at. % C offer a direct bandgap and strong optical emission, but energetic carbon sources such as plasmas and e-beam evaporation produce defective materials. In this work, we used CBr4 as a low-damage source of carbon in molecular beam epitaxy of tin-free GeC, with smooth surfaces and narrow x-ray diffraction peaks. Raman spectroscopy showed substitutional incorporation of C and no detectable sp2 bonding from amorphous or graphitic carbon, even without surfactants. Photoluminescence shows strong emission compared with Ge. [ABSTRACT FROM AUTHOR]

Direct bandgap group IV materials could provide intimate integration of lasers, amplifiers, and compact modulators within complementary metal–oxide–semiconductor for smaller, active silicon photonics. Dilute germanium carbides (GeC) with ∼1 at. % C offer a direct bandgap and strong optical emission, but energetic carbon sources such as plasmas and e-beam evaporation produce defective materials. In this work, we used CBr4 as a low-damage source of carbon in molecular beam epitaxy of tin-free GeC, with smooth surfaces and narrow x-ray diffraction peaks. Raman spectroscopy showed substitutional incorporation of C and no detectable sp2 bonding from amorphous or graphitic carbon, even without surfactants. Photoluminescence shows strong emission compared with Ge. [ABSTRACT FROM AUTHOR]

We demonstrate a non-monotonic evolution of in-plane thermal conductivity of large-area hexagonal boron nitride films with thickness. Wrinkles and defects/impurities are present in these films. Raman spectroscopy, an optothermal non-contact technique, is employed to probe the temperature and laser power dependence property of the Raman active E2ghigh phonon mode, which, in turn, is used to estimate the rise in the temperature of the films under different laser powers. As the conventional Fourier law of heat diffusion cannot be directly employed analytically to evaluate the thermal conductivity of these films with defects and wrinkles, finite-element modeling is used instead. In the model, average heat resistance is used to incorporate an overall near-surface defect structure, and Voronoi cells with contact resistance at the cell boundaries are constructed to mimic the wrinkled domains. The effective in-plane thermal conductivity is estimated to be 87, 55, and 117 W/m K for the 2, 10, and 30 nm-thick films, respectively. We also present a quantitative estimation of the thermal resistance by defects and wrinkles individually to the heat flow. Our study reveals that the defects/impurities render a much higher resistance to heat transfer in the films than wrinkles. [ABSTRACT FROM AUTHOR]

The binary Xe–Ar system has been studied in a series of high pressure diamond anvil cell experiments up to 60 GPa at 300 K. In-situ x-ray powder diffraction and Raman spectroscopy indicate the formation of a van der Waals compound, XeAr2, at above 3.5 GPa. Powder x-ray diffraction analysis demonstrates that XeAr2 adopts a Laves MgZn2-type structure with space group P63/mmc and cell parameters a = 6.595 Å and c = 10.716 Å at 4 GPa. Density functional theory calculations support the structure determination, with agreement between experimental and calculated Raman spectra. Our DFT calculations suggest that XeAr2 would remain stable without a structural transformation or decomposition into elemental Xe and Ar up to at least 80 GPa. [ABSTRACT FROM AUTHOR]

Fine-grained nuclear graphite is one of the key structural materials for high temperature gas-cooled reactors as well as several Generation IV nuclear fission reactor designs. However, its deformation and fracture behaviours at elevated temperatures are not well understood. In light of this, the current study focused on investigating the flexural strength and fracture toughness of two fine-grained graphite (SNG623 and T220) using real-time X-ray computed micro-tomography imaging at room temperature, 750 °C and 1100 °C. Specifically, nonlinear-elastic fracture mechanics-based JR(Δa) R-curves at these temperatures were presented with evolution of damage and failure micro-mechanisms, local strain distributions and J-integral fracture analysis, purveying notable findings. Compared to the coarser-grained Gilsocarbon nuclear graphites used in the current UK Advanced Gas-cooled Reactors (AGRs), these modern fine-grained graphites display deficient fracture resistance in the form of far less stable crack growth prior to catastrophic fracture and reduced failure strain at 1100 °C. Moreover, their elevation in strength and toughness at high temperatures is remarkably lower than that of Gilsocarbon graphite. Based on in situ high-temperature Raman spectroscopy mapping, we believe that one of the major causes of this behaviour can be attributed to the smaller magnitude of ‘frozen-in’ residual stress relaxed at elevated temperatures compared with Gilsocarbon graphite.

Abstract: 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, $${K}_{0}=46.9$$ K 0 = 46.9 GPa with an imposed value of $${K}_{0}^{\prime}= 4$$ K 0 ′ = 4 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 $${V}_{0}=322.2$$ V 0 = 322.2  Å3$$,$$ , $${K}_{0}=24.8$$ K 0 = 24.8 GPa and $${K}_{0}^{\prime}=4.0$$ K 0 ′ = 4.0 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.