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To reveal the pressure effects on BiOX semiconductors, we performed in-situ Raman spectroscopy and electrical transport measurements on BiOI up to 26.1 GPa and 19.2 GPa. BiOI showed good structural stability, while the electron conduction characteristics maintained dominance throughout the pressure range. The influence of grain boundary conduction disappeared at pressures above 9.2 GPa. With pressure elevation, the pressure-induced lattice fragmentation and grain refinement introduced a large number of relevant levels in the energy gap and resulted in a significant increase in the conductivity of BiOI under compression. The conductivity increased by 106 at 19.2 GPa from the initial value and maintained an increase of 102 after depressurization until ambient conditions were attained. At the same time, the space charge polarization of the crystal interface layer became weaker with pressure elevation resulting in a decrease in the relative permittivity of BiOI. The calculation results of the complex permittivity showed that the frequency of orientation polarization response decreases with pressure elevation, and the complex permittivity becomes constant in the high-frequency region. Our work proves that pressure could significantly increase the carrier concentration and mobility, thus effectively improving the conductivity of BiOX semiconductors.
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In this work, we prepared a BiOBr powder sample by the coprecipitation method for in situ high-pressure AC impedance spectroscopy tests, in situ high-pressure Raman measurements and in situ high-pressure X-ray diffraction experiments to explore its structural properties and electrical transport processes under compression. Two pressure-driven isostructural phase transitions, T-T' and T'-T'' (T - tetragonal, T' - tetragonal 1 and T'' - tetragonal 2), were discovered at around 10.0 and 15.0 GPa, respectively. The pressure-induced changes in the crystal structure and electrical transport of BiOBr can provide a reference for explaining the mechanism of the isostructural phase transition of other similar compounds after compression.
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The layered crystal of EuSn_{2}As_{2} has a Bi_{2}Te_{3}-type structure in rhombohedral (R3[over ¯]m) symmetry and has been confirmed to be an intrinsic magnetic topological insulator at ambient conditions. Combining ab initio calculations and in situ x-ray diffraction measurements, we identify a new monoclinic EuSn_{2}As_{2} structure in C2/m symmetry above â¼14 GPa. It has a three-dimensional network made up of honeycomblike Sn sheets and zigzag As chains, transformed from the layered EuSn_{2}As_{2} via a two-stage reconstruction mechanism with the connecting of Sn-Sn and As-As atoms successively between the buckled SnAs layers. Its dynamic structural stability has been verified by phonon mode analysis. Electrical resistance measurements reveal an insulator-metal-superconductor transition at low temperature around 5 and 15 GPa, respectively, according to the structural conversion, and the superconductivity with a T_{C} value of â¼4 K is observed up to 30.8 GPa. These results establish a high-pressure EuSn_{2}As_{2} phase with intriguing structural and electronic properties and expand our understandings about the layered magnetic topological insulators.
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In situ impedance measurement, resistivity measurements and first-principles calculations have been performed to investigate the effect of high pressure (up to 30.2 GPa) on the metallization and dielectric properties of GaP. It is found that the carrier transport process changes from mixed grain and grain boundary conduction to pure grain conduction at 5.8 GPa, and due to pressure-induced structural phase transition, the resistance drops drastically by three orders of magnitude at 25.5 GPa. Temperature dependence of resistivity measurements and band structure calculations suggest the occurrence of a semiconductor-metal transition. Combining differential charge density and dielectric analysis, it is observed that the electron localization is weakened, which leads to increased polarization and larger relative permittivity in the zb structure. After the phase transition, both the polarization and the relative permittivity decrease. Pressure increases the complex dielectric constant and dielectric loss factor, due to the increase in relaxation polarization and the scattering effect of carriers. Moreover, by comparing the high-pressure behavior of GaP, GaAs and GaSb, the changes in the electronic structure and electric transport process caused by the phase transition can be understood, which can enable us to better understand the metallization behavior and dielectric properties of Ga-based III-V family semiconductors under pressure, and stimulate the design and modification of other related group III-V semiconductors for optoelectronic devices and sensors.
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The ionic transport properties of solid electrolyte LaF3 were systematically studied under high pressures up to 30.6 GPa with alternate-current impedance spectra measurements and first-principles calculations. From the impedance spectra measurements, LaF3 was found to transform from pure ionic conduction to mixed ionic and electronic conduction at 15.0 GPa, which results from the pressure-induced structural phase transition from a tysonite-type structure to an anti-Cu3Ti-type structure. F- ion migration can be suppressed by pressure, causing a decrease of the ionic conductivity of LaF3. By first-principles calculations, the pressure-dependent diffusion behaviors of the F- ions can be understood. The increased overlap of electron clouds at the interstitial site between rigid La3+ and liquid F- lattices leads to the appearance of electronic conduction in anti-Cu3Ti-type structured LaF3.
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Herein we report two new TPE-based 3D MOFs, that is, Sr-ETTB and Co-ETTB (TPE=Tetraphenylethylene, H8 ETTB=4',4''',4''''',4'''''''-(ethene-1,1,2,2-tetrayl)tetrakis(([1,1'-biphenyl]-3,5-dicarboxylic acid))). Through tailoring outer shell electron configurations of SrII and CoII cations, the fluorescence intensity of the MOFs is tuned from high emission to complete non-emission. Sr-ETTB with strong blue fluorescence shows reversible fluorescence variations in response to pressure and temperature, which is directly related to the reversible deformation of the crystal structure. In addition, non-emissive Co-ETTB counterpart exhibits a turn-on fluorescent enhancement under the stimulation of analyte histidine. In the process, TPE-cored linkers in the MOFs are released through competitive coordination substitution and subsequently reassembled to perform aggregation-induced luminescence behavior originated from the organic linkers.
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At ambient conditions, the lattice structure of supported ultrathin transition metal dichalcogenides (TMDs) can be effectively modified by a substrate. When compressed, the effect of substrate is far from settled. In this study, the effects of an Si substrate on the lattice structures of compressed monolayer and multilayer ReS2 were investigated by performing high-pressure Raman measurements and first-principle calculations. Our results revealed substrate-affected strain in compressed monolayer ReS2, which resulted in a distorted unit with S atoms sliding within a single layer. This was evidenced by the split of the Ag-5 mode above 1.7 GPa. However, unlike that of the monolayer ReS2, the Ag-5 mode of multilayer ReS2 remained symmetric up to 4.2 GPa, which can be due to weaker substrate-affected strain in compressed multilayer ReS2 when compared with that in the monolayer ReS2. The noticeably different high-pressure responses between multilayer ReS2 and monolayer ReS2 can be due to the effect of interlayer interactions, and the split of the Ag-5 mode provides a clear indication of the prominent strain in compressed supported ReS2.
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The electrical transport behavior of the superionic conductor AgBr was systematically studied under high pressure up to 30.0 GPa with electrochemical impedance spectra measurements and first-principles calculations. From impedance spectra measurements, a pressure-induced abnormal ionic-polaronic-ionic transition was found. Herein, the ionic to polaronic transition at 5.0 GPa occurs with the absence of a structural phase transition. At 8.6 GPa, the ionic state of AgBr can be reactivated after a structural phase transition. Previous structural studies based on X-ray diffraction data cannot provide strong evidence to support the ionic-polaronic transition in AgBr at 5.0 GPa. In this paper, based on first-principles calculations, a localized-electron-soup model was proposed to explain the physical origin of the ionic-polaronic transition. In this model, more localized electrons around the Br atoms are pressed into interstitial spaces and, simultaneously, polarons are formed between Ag+ ions and the localized electron background at 5.0 GPa. Therefore, the diffusion of Ag+ ions is effectively screened by the movement of the localized electron background from its equilibrium position, much like beans completely trapped in a cup of thick soup.
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Hydride ions (H-) have an appropriate size for fast transport, which makes the conduction of H- attractive. In this work, the H- transport properties of BaH2 have been investigated under pressure using in situ impedance spectroscopy measurements up to 11.2 GPa and density functional theoretical calculations. The H- transport properties, including ionic migration resistance, relaxation frequency, and relative permittivity, change significantly with pressure around 2.3 GPa, which can be attributed to the structural phase transition of BaH2. The ionic migration barrier energy of the P63/mmc phase decreases with pressure, which is responsible for the increased ionic conductivity. A huge dielectric constant at low frequencies is observed, which is related to the polarization of the H- dipoles. The current study establishes general guidelines for developing high-energy storage and conversion devices based on hydride ion transportation.
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In situ impedance measurements were employed to investigate the electrical transport properties of BaMoO4 under pressures of up to 20.0 GPa. Two anomalous changes in the electrical parameters were found, related to the pressure-induced structural phase transitions. The dielectric performance of BaMoO4 was improved by pressure. The dispersion in the real part of dielectric constant versus frequency weakens with increasing pressure. Based on the first-principles calculations, the increases of resistance with increasing pressure in the tetragonal and monoclinic phases were mainly caused by the increasing defect levels. The decrease of the relative permittivity in the tetragonal phase was attributed to pressure-induced strengthening in electronic localization around Mo atoms, which hindered the polarization of Mo-O electric dipoles.
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In this work, we report the pressure-dependent electrical transport and structural properties of SnSe. In our experiments an electronic transition from a semiconducting to semimetallic state was observed at 12.6 GPa, followed by an orthorhombic to monoclinic structural transition. Hall effect measurements indicate that both the carrier concentration and mobility vary abnormally accompanied by the semimetallic electronic transition. First-principles band structure calculations confirm the semiconducting-semimetallic transition, and reveal that the semimetallic character of SnSe can be attributed to the enhanced coupling of Sn-5s, Sn-5p, and Se-3p orbitals under compression that results in the broadening of energy bands and subsequently the closure of the band gap. The pressure modulated variations of electrical transport and structural properties may provide an approach to improving the thermoelectric properties of SnSe.
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Herein, we report on the intriguing electrical transport properties of compressed AlAs. The relative permittivity and the resistances of both the grain and bulk boundaries vary abnormally at â¼10.9 GPa, accompanied by the cubic-hexagonal structural transition of AlAs. With further compression, the boundary effect becomes undistinguished, and subsequently, the electrical transport mechanism converts from boundary- to bulk-dominated, which gives rise to a significant reduction in the total resistance of AlAs. After being quenched to ambient pressure, resistances recover to the initial values followed by the re-emergence of the boundary effect. Eg decreases with pressure and its pressure dependence changes at â¼14.0 GPa, which rationalizes the anomalous variation of the electrical transport properties. The experimental results indicate that the boundary effect can be modulated by compression and increases the resistance difference between the two states. This opens up a new possible basis for optimizing the performance of AlAs-based applications, including multilevel phase-change memories.
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The phase diagram of water near the ice VI-ice VII-liquid triple point and electrical transport properties of these ices have been studied by in situ electrical conductivity measurements in a diamond anvil cell. The obtained phase boundary between ices VI and VII and the melting curve for these ices are in accord with most previous results. The different properties and amount of orientational defects in ice VI and ice VII are associated with abrupt changes in conductivity when a phase transition from ice VI to ice VII occurs. The electrical transport mechanisms of these two ice polymorphs can be understood in terms of the conduction of the already existing ions and Bjerrum defects.
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The measurements of temperature directly influence the reasonability of experiments at high pressure and high temperature. In this article, we proposed a new integration design, the built-in thermocouple, for in situ temperature measurements in high-pressure-high-temperature experiments by fusing the characteristics of thermocouples and diamond anvil cells together. By integrating an S-type thermocouple inside the gasket of a diamond anvil cell, we successfully measured the temperature of the sample straight inside the pressure chamber at high pressure and high temperature. The setup underwent multiple experimental tests using internal and external heating techniques, the results of which revealed its capability to directly characterize the temperature of the sample with comparable accuracy and reliability to that of the typical external thermocouple setup. The proposed setup has also resolved the issue of the discrepancy of temperatures inside and outside the sample chamber and enormously expedited the temperature measurements by significantly reducing the response time of the thermocouple. In conclusion, the built-in thermocouple is a promising approach toward high-efficiency, in situ temperature measurements under extreme conditions.
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In high-pressure experimental methods, sample heating in the pressure chamber of a diamond anvil cell is an important topic, and numerous efforts have been made to improve and develop new technologies. In this paper, we propose a new type of internal resistance heating technique, the composite heating gasket, prepared by integrating an annular heater into the sample chamber for direct heating of the sample. As the effective heating area covers the entire pressure chamber wall, a relatively quasi-uniform temperature field is formed within the sample chamber. At the same time, the integration design reduces the risk of diamond oxidation and enables direct measurement of the spectroscopic properties of samples at high temperatures. The preparation of the composite heating gasket is simple and repeatable, and its heating performance is stable at temperatures above 1400 K. When the sample diameter is 210 µm and no thermal insulation is used, the diameter of the temperature zone in which the temperature difference is less than 10 and 20 K exceeds 120 and 170 µm, respectively. The composite heating gasket represents a significant advancement in providing a uniform temperature field for in situ measurements with diamond anvil cells at high pressure and temperature.
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An accurate in situ electrical resistivity measurement of cuprous oxide cubes has been conducted in a diamond anvil cell at room temperature with pressures up to 25 GPa. The abnormal electrical resistivity variation found at 0.7-2.2 GPa is attributed to the phase transformation from a cubic to a tetragonal structure. Three other discontinuous changes in the electrical resistivity are observed around 8.5, 10.3, and 21.6 GPa, corresponding to the phase transitions from tetragonal to pseudocubic to hexagonal to another hexagonal phase, respectively. The first-principles calculations illustrate that the electrical resistivity decrease of the tetragonal phase is not related to band-gap shrinkage but related to a higher quantity of electrons excited from strain-induced states increasing in band gap with increasing pressure. The results indicate that the Cu(2)O cubes begin to crush at about 15 GPa and completely transform into nanocrystalline at 25 GPa.
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Temperature induced pressure drift in the diamond anvil cell (DAC) is a major issue in high-pressure high-temperature experiments. It is commonly acknowledged that these drifts originate from multiple factors, but no systematic descriptions have been made so far. By introducing an internal water-cooling system in the DAC, we have performed a systematic investigation into temperature induced pressure drifts to reveal the mechanism behind them and to find a proper experimental procedure to achieve minimal pressure variation in DAC's heating experiment. It is revealed in this experiment that pressure variation during heating processes originates from multiple temperature related factors of the DAC. The variation itself can be considered as a rebalancing process of the compression forces on the sample chamber initiated by the disturbance caused by temperature elevation. It is possible to suppress pressure variation by maintaining the temperature of the DAC body at room temperature to ensure the consistency of compression on the sample chamber. At the same time, the best procedure for the heating experiments is to properly pre-heat the sample chamber equipped with the internal water-cooling system before performing the in situ measurements on the temperature-related properties at the pressurized and heated conditions. Our discovery provides a reliable procedure for the sample heating process in the DAC and helps resolve the complex mystery of the influence of the combination of pressure and temperature in high-pressure high-temperature experiments.
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Impedance spectroscopy (IS) is an indispensable method of exploring electrical properties of materials. In this review, we provide an overview on the specific applications of IS measurement in the investigations of various electrical properties of materials under high pressure, including electric conduction in bulk and grain boundary, dielectric properties, ionic conduction, and electrostrictive effect. Related studies are summarized to demonstrate the method of analyzing different electrical transport processes with various designed equivalent circuits of IS and reveal some interesting phenomena of electrical properties of materials under high pressure.
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In general, pressure calibration in diamond anvil cells (DACs) has been achieved by mixing pressure calibration materials (PCMs) with the sample inside the pressure chamber. However, the chemical reactions between the sample and PCMs are sometimes unavoidable at extreme conditions, such as high pressure and high temperature. These undesired reactions will cause pollution, induce changes in physical properties or phase transformations of PCMs, and result in tremendous error of pressure calibration. In this paper, we report a new design of DAC with double coaxial pressure chambers, sample and PCM chambers, to resolve the challenge by isolating the PCM from the sample. Our test results show that the pressure of the two chambers presents interesting relations with the anvil setup. When the geometric parameters of two anvil sets are the same and the difference of chamber diameters is within a certain range (i.e., below 10 µm), the pressure correlation between the two chambers shows little correlation with the pressure transmitting medium before and after its solidification at both room temperature and high temperatures within the experimental condition range (well below 20 GPa and 634 K). In this case, the pressure of the sample chamber can be well calibrated by the pressure of the PCM chamber. This new DAC setup is thus proved to be effective in calibrating the sample pressure below certain conditions while avoiding undesired sample pollution and pressure induced property changes in PCMs under high pressure and high temperature conditions compared with single-chamber DACs.
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The electrical transport and structural properties of tin oxide nanoparticles under compression have been studied by in situ impedance measurements and synchrotron X-ray diffraction (XRD) up to 27.9 GPa. It was found that the conduction of SnO2 can be improved significantly with compression. Abnormal variations in resistivity, relaxation frequency, and relative permittivity were observed at approximately 12.3 and 25.0 GPa, which can be attributed to pressure-induced tetragonal- orthorhombic-cubic structural transitions. The dielectric properties of the SnO2 nanoparticles were found to be a function of pressure, and the dielectric response was dependent on frequency and pressure. The dielectric constant and loss tangent decreased with increasing frequency. Relaxation-type dielectric behaviour dominated at low frequencies. Whereas, modulus spectra indicated that charge carrier short-range motion dominated at high frequencies.