Pressure-induced Structural Changes Research Articles

Pressure-Induced Effects in Organic-Inorganic Hybrid Perovskites.

In this Perspective, we provide an overview of the pressure-induced effects on hybrid organic-inorganic perovskite for photovoltaics applications. It is shown that a fine-tuning of the most relevant photovoltaic properties, including band gap and carrier lifetime, is indeed possible by applying pressure over a rather small range and that such phenomena closely correlate with pressure-induced structural changes. High-pressure research can be used to search for new materials since the high-pressure structural configuration can be used as a model for tailoring ambient pressure compounds under proper chemical substitution, and the band gap tuning and enhancement of carrier lifetime with applied pressures can be a guide to design new hybrid perovskites with desired optical properties as a function of structural parameters.

Isotactic poly(4-methyl-1-pentene) melt as a porous liquid: Reduction of compressibility due to penetration of pressure medium.

A pressure-induced structural change of a polymer isotactic poly(4-methyl-1-pentene) (P4MP1) in the melted state at 270 °C has been investigated by high-pressure in situ x-ray diffraction, where high pressures up to 1.8 kbar were applied using helium gas. The first sharp diffraction peak (FSDP) position of the melt shows a less pressure dependence than that of the normal compression using a solid pressure transmitting medium. The contraction using helium gas was about 10% at 2 kbar, smaller than about 20% at the same pressure using a solid medium. The result indicates that helium entered the interstitial space between the main chains. The helium/monomer molar ratio was estimated to be 0.3 at 2 kbar from the FSDP positions. These results suggest that the compressibility of the P4MP1 melt can be largely dependent on the pressure transmitting media. As the pore size is reversibly and continuously controllable by compression, we suggest that the P4MP1 melt can be an ideal porous liquid for investigating a novel mechanical response of the pores in a non-crystalline substance.

Pressure-induced electronic topological transitions in the charge-density-wave material In4Se3

High-pressure in situ angle dispersive X-ray diffraction (ADXRD) measurements were performed on the charge-density-wave (CDW) material In4Se3 up to 48.8 GPa. Pressure-induced structural changes were observed at 7.0 and 34.2 GPa, respectively. Using the CALYPSO methodology, the first high-pressure phase was solved as an exotic Pca21 structure. The compressional behaviors of the initial Pnnm and the Pca21 phases were all determined. Combined with first-principle calculations, we find that, unexpectedly, the Pnnm phase probably experiences twice electronic topological transitions (ETTs), from the initial possible CDW state to a semimetallic state at about 2.3 GPa and then back to a possible CDW state at around 3.5 GPa, which was uncovered for the first time in CDW systems. In the both possible CDW states, pressure provokes a decrease of band-gap. The observation of a bulk metallic state was ascribed to structural transition to the Pca21 phase. Besides, based on electronic band structure calculations, the thermoelectric property of the Pnnm phase under compression was discussed. Our results show that pressure play a dramatic role in tuning In4Se3's structure and transport properties.

Pressure-induced structural change in liquid GaIn eutectic alloy

Synchrotron x-ray diffraction reveals a pressure induced crystallization at about 3.4 GPa and a polymorphic transition near 10.3 GPa when compressed a liquid GaIn eutectic alloy up to ~13 GPa at room temperature in a diamond anvil cell. Upon decompression, the high pressure crystalline phase remains almost unchanged until it transforms to the liquid state at around 2.3 GPa. The ab initio molecular dynamics calculations can reproduce the low pressure crystallization and give some hints on the understanding of the transition between the liquid and the crystalline phase on the atomic level. The calculated pair correlation function g(r) shows a non-uniform contraction reflected by the different compressibility between the short (1st shell) and the intermediate (2nd to 4th shells). It is concluded that the pressure-induced liquid-crystalline phase transformation likely arises from the changes in local atomic packing of the nearest neighbors as well as electronic structures at the transition pressure.

Pressure-induced changes in the electronic structure and enhancement of the thermoelectric performance of SnS2: a first principles study

Hydrostatic pressure reduces the band gap and increases the ZT value of SnS2.

Pressure-induced effects on the spectroscopic properties of Nd3+ in MgO:LiNbO3 single crystal. A crystal field approach

The effects of pressure on the Nd3+-doped MgO:LiNbO3 single crystal have been studied by luminescence spectroscopy at low temperature and high pressures from ambient conditions up to 33GPa. Specifically, the pressure-induced evolution of the emission spectra, corresponding to the 4F3/2→4I9/2,4I11/2 transitions, and the excitation spectra, corresponding to the 4I9/2→4F5/2+2H9/2, and 4I9/2→4F7/2+4S3/2 transitions, show a gradual red-shift that follows a linear pressure dependence and a decrease in the intensity of the spectra with increasing pressure. The initial effect of increasing pressure on the MgO:LiNbO3 crystal is the modification of the relative amount of the several centers in the sample. At pressures around 20GPa the characteristic multicenter Nd3+ structure eventually disappears indicating that all the centers have very similar environments near this pressure. At higher pressures, observed changes seem to have a different origin. The evolution of Nd3+ luminescence is studied in the frame of crystal-field theory in order to evaluate its capability of monitoring the pressure-induced structural changes. Crystal-field analysis, under approximated C3v symmetry, shows a smooth increase of the overall crystal-field strength on the luminescent ion, which can be related to the volume reduction as pressure increases. Crystal-field parameters also show a general monotonic behavior with pressure that indicates a structural modification of the local structure that, maintaining the trigonal symmetry around the impurity ion, evolves towards a lower axial character. No evidences of a phase transition have been observed in the studied pressure range.

High-Pressure Structural Response of an Insensitive Energetic Crystal: 1,1-Diamino-2,2-dinitroethene (FOX-7)

High-pressure structural response of an insensitive energetic crystal—1,1-diamino-2,2-dinitroethene (FOX-7)—was examined to gain insight into its structural and chemical stability and to obtain isothermal compression data. Using synchrotron single-crystal X-ray diffraction measurements, details of pressure-induced structural changes to 12.8 GPa were determined across three FOX-7 phases: α (P21/n), α′ (P21/n), and e (P1). We found that the C–NO2 bond is the most compressible chemical bond, and high pressure significantly reduces and homogenizes the length of H bonds in the hydrogen-bond network. The α′−e phase transition, at 4.5 GPa, significantly affects all molecular and crystal properties, whereas the α–α′ transition, at 2 GPa, is associated with subtle molecular and intermolecular changes. Anisotropic compressibility was observed over the entire pressure range, consistent with the layered structure of the crystal. The equation-of-state parameters were obtained using the third-order Birch–Murnaghan equa...

High-pressure Seebeck coefficients and thermoelectric behaviors of Bi and PbTe measured using a Paris-Edinburgh cell

A new sample cell assembly design for the Paris-Edinburgh type large-volume press for simultaneous measurements of X-ray diffraction, electrical resistance, Seebeck coefficient and relative changes in the thermal conductance at high pressures has been developed. The feasibility of performing in situ measurements of the Seebeck coefficient and thermal measurements is demonstrated by observing well known solid-solid phase transitions of bismuth (Bi) up to 3 GPa and 450 K. A reversible polarity flip has been observed in the Seebeck coefficient across the Bi-I to Bi-II phase boundary. Also, successful Seebeck coefficient measurements have been performed for the classical high-temperature thermoelectric material PbTe under high pressure and temperature conditions. In addition, the relative change in the thermal conductivity was measured and a relative change in ZT, the dimensionless figure of merit, is described. This new capability enables pressure-induced structural changes to be directly correlated to electrical and thermal properties.

Ab Initio Study of Elastic Properties of High-Pressure Polymorphs of CO2 Phases II and V

Elastic properties of prototypical CO2 polymorphs under compression are essential to understanding the nature of their pressure-induced structural changes. Despite the fundamental importance in physical chemistry and condensed matter physics and geophysical implications for the nature of fluids in the Earth and planetary interiors, the elastic properties of these polymorphs are not fully understood because of intrinsic uncertainty and difficulties in experimental estimation of elasticity. Theoretical calculations of elastic properties of high-pressure CO2 polymorphs allow us to reveal the previously unknown details of elasticity of the diverse polymorphs under extreme compression. As a step toward getting insights into the deep carbon cycle, we carried out density-functional-theory calculations and investigated the elastic constants, bulk modulus, shear modulus, Poisson ratios and acoustic wave velocities of CO2 polymorphs: II (tetragonal, P42/mnm), β-cristobalite-like V (VCR, tetragonal, I42d) and tridy...

High-pressure Raman study of Terephthalonitrile

The in situ high-pressure Raman spectra of Terephthalonitrile (TPN) have been investigated from ambient to 12.6GPa at room temperature. All the fundamental vibrational modes of TPN at ambient were assigned based on the first-principle calculations. A detailed Raman spectroscopy analysis revealed that TPN underwent a phase transition at ~5.3GPa. The frequencies of the TPN Raman peaks increase with increasing the pressure which can be attributed to the reduction in the interatomic distances and the escalation of effective force constants. The intensity of the C-C-C ring-out-plane deformation mode increases gradually as the frequency remains almost constant during the compression which can be explained by the existence of π-π interactions in TPN molecules. Additionally, the pressure-induced structural changes of TPN on the Fermi resonance between the C≡N out-of-plane vibration mode and the C−CN out-of-plane vibration mode have been analyzed.

Atomistic origins of pressure-induced changes in the OK-edge x-ray Raman scattering features ofSiO2andMgSiO3polymorphs: Insights fromab initiocalculations

Despite its fundamental importance in condensed matter physics and geophysical implications, establishing the systematic and direct link between the pressure-induced structural changes in crystalline and noncrystalline low-$z$ oxides and their corresponding evolution in O $K$-edge core-electron excitation features under extreme compression has been challenging. Here we calculated the site-resolved partial density of states and O $K$-edge x-ray Raman scattering (XRS) spectra for two of the important oxide phases in the Earth's lower mantle, $\mathrm{MgSi}{\mathrm{O}}_{3}$ bridgmanite and post-bridgmanite, up to 120 GPa using ab initio calculations, revealing the electronic origins of the O $K$-edge features for oxides under compression. The absorption threshold $({E}_{A})$ and band gap increase linearly with a decrease in the O-O distance in diverse $\mathrm{Si}{\mathrm{O}}_{2}$ and $\mathrm{MgSi}{\mathrm{O}}_{3}$ high-pressure phases $[{E}_{A}(\mathrm{eV})\ensuremath{\approx}\ensuremath{-}10.9{d}_{\text{O-O}}(\AA{})+34.4]$, providing a predictive relationship between the ${E}_{A}$ and the O-O distances in the oxide at high pressure. Despite densification, upon isobaric phase transition from bridgmanite to post-bridgmanite at 120 GPa, a decrease in band gap results in a decrease in edge energy because of an increase in O-O distance. The oxygen proximity is a useful structural proxy of oxide densification upon compression, as it explains the pressure-induced changes in O $K$-edge XRS features of crystalline and amorphous $\mathrm{Si}{\mathrm{O}}_{2}$ and $\mathrm{MgSi}{\mathrm{O}}_{3}$ at high pressures. These results can be applied to studies of the pressure-bonding transitions in a wide range of oxides under extreme compression.

Molecular dynamics simulations of pressure-induced structural and mechanical property changes in amorphous Al2O3

Molecular dynamics (MD) simulations of amorphous alumina have been carried out to investigate the pressure-induced structural transformation and mechanical properties. We found that not only the fraction of units AlOx (x=4, 5, 6) but also the density of each AlOx type change upon compression. The density of sample can be expressed through the fraction and partial density of units AlOx. With increasing pressure, O atoms are more ordered than Al atoms and form fcc and hcp clusters. The same units AlOx link together to form atomic clusters (AC) of type AC4, AC5 and AC6 (AC4, AC5 and AC6 consist of units AlO4, AlO5 and AlO6, respectively). The Young's modulus can also be expressed through the fraction and partial Young's modulus of units AlOx.

Pressure dependence of the electronic structure of 4f and 3d electron systems studied by X-ray emission spectroscopy

ABSTRACTTechniques based on X-ray emission spectroscopy (XES) have been utilized to investigate pressure-induced changes in the electronic structure in samples subject to high pressure in the diamond anvil cell. High-resolution X-ray absorption spectra can be obtained with partial fluorescence yield mode (PFY-XAS) measurement. As typical examples, we show results of measurements of the valence fluctuating systems of CeCuGe, Ce115 systems, and YbNiGe. The pre-edge feature of the XAS spectra at K-absorption edge of 3d-elements correlates to the spin states. We also show the results of the Fe XES and PFY-XAS of KFeSe, which has two pressure-induced superconducting (SC) domes.

Ultrahigh-pressure acoustic wave velocities of SiO2-Al2O3 glasses up to 200 GPa

Extensive experimental studies on the structure and density of silicate glasses as laboratory analogs of natural silicate melts have attempted to address the nature of dense silicate melts that may be present at the base of the mantle. Previous ultrahigh-pressure experiments, however, have been performed on simple systems such as SiO2 or MgSiO3, and experiments in more complex system have been conducted under relatively low-pressure conditions below 60 GPa. The effect of other metal cations on structural changes that occur in dense silicate glasses under ultrahigh pressures has been poorly understood. Here, we used a Brillouin scattering spectroscopic method up to pressures of 196.9 GPa to conduct in situ high-pressure acoustic wave velocity measurements of SiO2-Al2O3 glasses in order to understand the effect of Al2O3 on pressure-induced structural changes in the glasses as analogs of aluminosilicate melts. From 10 to 40 GPa, the transverse acoustic wave velocity (V S ) of Al2O3-rich glass (SiO2 + 20.5 mol% Al2O3) was greater than that of Al2O3-poor glass (SiO2 + 3.9 mol% Al2O3). This result suggests that SiO2-Al2O3 glasses with higher proportions of Al ions with large oxygen coordination numbers (5 and 6) become elastically stiffer up to 40 GPa, depending on the Al2O3 content, but then soften above 40 GPa. At pressures from 40 to ~100 GPa, the increase in V S with increasing pressure became less steep than below 40 GPa. Above ~100 GPa, there were abrupt increases in the P-V S gradients (dV S /dP) at 130 GPa in Al2O3-poor glass and at 116 GPa in Al2O3-rich glass. These changes resemble previous experimental results on SiO2 glass and MgSiO3 glass. Given that changes of dV S /dP have commonly been related to changes in the Si-O coordination states in the glasses, our results, therefore, may indicate a drastic structural transformation in SiO2-Al2O3 glasses above 116 GPa, possibly associated with an average Si-O coordination number change to higher than 6. Compared to previous acoustic wave velocity data on SiO2 and MgSiO3 glasses, Al2O3 appears to promote a lowering of the pressure at which the abrupt increase of dV S /dP is observed. This suggests that the Al2O3 in silicate melts may help to stabilize those melts gravitationally in the lower mantle.

Suppression of Jahn-Teller Distortions and Origin of Piezochromism and Thermochromism in Cu-Cl Hybrid Perovskite.

While pressure-induced changes in the electronic, magnetic, and optical properties of Cu-Cl hybrid perovskites have been studied intensively, the correlation between these properties and pressure-induced structural changes is still vaguely understood. Here, by first-principles calculations on a model system (EDBE)[CuCl4] (EDBE = 2,2'-(ethylenedioxy)bis(ethylammonium)) (a Cu-Cl hybrid perovskite), we correlate the evolution of a series of exciting physical properties with pressure while resolving some of the long-standing debates on the fundamental electronic nature of this important class of material. The material shows two structural phase transitions and an anisotropy in compressibility with increasing pressure. After a critical pressure of 17 GPa, the structure becomes highly symmetric, thereby suppressing the Jahn-Teller distortions. At zero pressure, mapping the optical transitions with the Laporte selection rules, lower and higher energy excitations are found to be of Mott-Hubbard (MH) and charge transfer (CT) type, respectively, signifying the material to be a Mott insulator. The material shows a red shift in the charge transfer band edge with increasing pressure and temperature, demonstrating the piezochromism and the thermochromism, respectively. Piezochromism originates from the changes in mixing of Cl-Cu p-d states, while thermochromism is due to broadening of conduction band states, thereby showing different electronic and structural evolution with pressure and temperature. Furthermore, the magnetic ordering in the material was found to be stable up to higher pressures, making pressure a tool to tune the electronic property without perturbing the magnetic property.

Three-dimensional visualisation of soft biological structures by X-ray computed micro-tomography.

Whereas the two-dimensional (2D) visualisation of biological samples is routine, three-dimensional (3D) imaging remains a time-consuming and relatively specialised pursuit. Current commonly adopted techniques for characterising the 3D structure of non-calcified tissues and biomaterials include optical and electron microscopy of serial sections and sectioned block faces, and the visualisation of intact samples by confocal microscopy or electron tomography. As an alternative to these approaches, X-ray computed micro-tomography (microCT) can both rapidly image the internal 3D structure of macroscopic volumes at sub-micron resolutions and visualise dynamic changes in living tissues at a microsecond scale. In this Commentary, we discuss the history and current capabilities of microCT. To that end, we present four case studies to illustrate the ability of microCT to visualise and quantify: (1) pressure-induced changes in the internal structure of unstained rat arteries, (2) the differential morphology of stained collagen fascicles in tendon and ligament, (3) the development of Vanessa cardui chrysalises, and (4) the distribution of cells within a tissue-engineering construct. Future developments in detector design and the use of synchrotron X-ray sources might enable real-time 3D imaging of dynamically remodelling biological samples.

Universal amorphous-amorphous transition in GexSe100-x glasses under pressure.

Pressure induced structural modifications in vitreous GexSe100−x (where 10 ≤ x ≤ 25) are investigated using X-ray absorption spectroscopy (XAS) along with supplementary X-ray diffraction (XRD) experiments and ab initio molecular dynamics (AIMD) simulations. Universal changes in distances and angle distributions are observed when scaled to reduced densities. All compositions are observed to remain amorphous under pressure values up to 42 GPa. The Ge-Se interatomic distances extracted from XAS data show a two-step response to the applied pressure; a gradual decrease followed by an increase at around 15–20 GPa, depending on the composition. This increase is attributed to the metallization event that can be traced with the red shift in Ge K edge energy which is also identified by the principal peak position of the structure factor. The densification mechanisms are studied in details by means of AIMD simulations and compared to the experimental results. The evolution of bond angle distributions, interatomic distances and coordination numbers are examined and lead to similar pressure-induced structural changes for any composition.

Electromodulation spectroscopy of direct optical transitions in Ge1−xSnx layers under hydrostatic pressure and built-in strain

Unstrained Ge1−xSnx layers of various Sn concentration (1.5%, 3%, 6% Sn) and Ge0.97Sn0.03 layers with built-in compressive (ε = −0.5%) and tensile (ε = 0.3%) strain are grown by molecular beam epitaxy and studied by electromodulation spectroscopy (i.e., contactless electroreflectance and photoreflectance (PR)). In order to obtain unstrained GeSn layers and layers with different built-in in-plane strains, virtual InGaAs substrates of different compositions are grown prior to the deposition of GeSn layers. For unstrained Ge1−xSnx layers, the pressure coefficient for the direct band gap transition is determined from PR measurements at various hydrostatic pressures to be 12.2 ± 0.2 meV/kbar, which is very close to the pressure coefficient for the direct band gap transition in Ge (12.9 meV/kbar). This suggests that the hydrostatic deformation potentials typical of Ge can be applied to describe the pressure-induced changes in the electronic band structure of Ge1−xSnx alloys with low Sn concentrations. The same conclusion is derived for the uniaxial deformation potential, which describes the splitting between heavy-hole (HH) and light-hole (LH) bands as well as the strain-related shift of the spin-orbit (SO) split-off band. It is observed that the HH, LH, and SO related transitions shift due to compressive and tensile strain according to the Bir-Pikus theory. The dispersions of HH, LH, and SO bands are calculated for compressive and tensile strained Ge0.97Sn0.03 with the 8-band kp Hamiltonian including strain effects, and the mixing of HH and LH bands is discussed. In addition, the dispersion of the electronic band structure is calculated for unstrained Ge1−xSnx layers (3% and 6% Sn) at high hydrostatic pressure with the 8-band kp Hamiltonian, and the pressure-induced changes in the electronic band structure are discussed.

Pressure-Induced Structural Transition Trends in Nanocrystalline Rare-Earth Sesquioxides: A Raman Investigation

The article presents a concise review of our investigations on the preferred transition paths followed as well as high-pressure-induced structural changes in nanocrystalline rare-earth sesquioxides that include Y2O3, Sm2O3, Gd2O3, Eu2O3, Dy2O3, Ho2O3, and Yb2O3. The starting phase in all samples was predominantly cubic, as characterized using X-ray diffraction and Raman spectroscopy. The pressure-induced structural changes were primarily tracked via changes in phonon modes in the Raman spectra. The structural transition sequences demonstrated behaviors differing from the polycrystalline trends usually observed; however, it was interesting to note that the onset pressures and subsequent shifts in the phonon modes followed a trend similar to the unpressurized samples when observed with respect to the f-electron number. The mode Gruneisen parameters were estimated from the high-pressure data, which indicated a swifter response to external stimuli as the particle size reduced below an average of 50 nm. It was...

Temperature- and Pressure-Induced Structural Changes of Cobalt(II) in a Phosphonium-Based Ionic Liquid

The temperature- and pressure-induced paramagnetic switching of cobalt(II) complex in a binary mixture of phosphonium-based ionic liquid [P6,6,6,14]SCN and [Co(NCS)2] is reported. This arises from a structural change in the coordination of the cobalt(II) center from tetrahedral [Co(NCS)4]2– to octahedral [Co(NCS)6]4– when mobile thiocyanate ions are added. These properties are reflected in the abrupt change of the conductivity behavior of the magnetic ionic liquid. Therefore, as demonstrated herein, the reversible switching in coordination of cobalt from tetrahedral to octahedral can be easily monitored at ambient as well as elevated pressure by tracking the dc-conductivity changes.