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The absence of intrinsic p-type 2D layered semiconductors has hampered the development of 2D devices, particularly in complementary metal-oxide-semiconductor (CMOS) devices and integrated circuits. Developing practical p-type semiconductors and advanced modulation techniques for precise carrier control is paramount to advancing electronic devices and systems. Here, by applying pressure to continuously tune the Peierls distortion in NbOI2, we effectively control the polarity and concentration of carriers and significantly enhance its photoelectric properties. The results demonstrate that by suppressing the off-center displacement of Nb atoms along the in-plane b direction under pressure, NbOI2 undergoes a semiconductor-to-semiconductor phase transition from C2 to C2/m, leading to a significant transition from n-type to p-type carrier behavior. Additionally, the gradual inhibition of internal interactions within Nb-Nb dimers along the in-plane c direction under high pressure facilitates electron delocalization, substantially enhancing the photoelectric properties. The photocurrent is increased by more than 3 orders of magnitude under xenon irradiation, and the spectral response range is continuously red-shifted and extended to 1450 nm. These findings highlight the potential of pressure engineering to adjust photoelectric properties effectively and flexibly, offering valuable insights for designing high-performance p-type two-dimensional semiconductors.
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It is urgent to develop a polyamide (PA) thin-film composite (TFC) membrane with a new method in this study by designing and constructing a new nanomaterial support layer instead of the conventional support layer. Polydopamine-wrapped single-walled carbon nanotubes (PDA@MWCNTs) as the place of the polymerization reaction can optimize the PA film structure and performance. The resulting composite membrane presents a higher water flux of 15.8 L·m-2·h-1·bar-1 and a rejection rate of 97% to Na2SO4, simultaneously maintaining this high separation performance in 300 min. It is a new ideal to construct novel support layer by using inorganic nanoparticles and organic polymer nanofiber membranes.
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The discovery of superconductivity in twisted bilayer graphene has reignited enthusiasm in the field of flat-band superconductivity. However, important challenges remain, such as constructing a flat-band structure and inducing a superconducting state in materials. Here, we successfully achieved superconductivity in Bi2O2Se by pressure-tuning the flat-band electronic structure. Experimental measurements combined with theoretical calculations reveal that the occurrence of pressure-induced superconductivity at 30 GPa is associated with a flat-band electronic structure near the Fermi level. Moreover, in Bi2O2Se, a van Hove singularity is observed at the Fermi level alongside pronounced Fermi surface nesting. These remarkable features play a crucial role in promoting strong electron-phonon interactions, thus potentially enhancing the superconducting properties of the material. These findings demonstrate that pressure offers a potential experimental strategy for precisely tuning the flat band and achieving superconductivity.
RESUMEN
Microstructure transformation of materials under compression is crucial to understanding their high-pressure phase transformation. However, direct observation of the microstructure of compressive materials is a considerable challenge, which impedes the understanding of the relations among phase transformation, microstructure, and material properties. In this study, we used transmission Kikuchi diffraction and transmission electron microscopy to intuitively characterize pressure-induced phase transformation and microstructure of TiO2. We observed the changes of twin boundaries with increasing pressure and intermediate phase TiO2-I of anatase transformed into TiO2-II (α-PbO2 phase) for the first time. The following changes occur during this transformation: anatase (diameter of â¼100 nm) â anatase twins 60° along the [110] zone axis â intermediate TiO2-I twins 60° along the [010] zone axis â TiO2-II twins 90° along the [010] zone axis. These results directly reveal the crystallographic relation among these structures, enhancing our understanding of the phase transformation in TiO2 nanocrystals.
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Simultaneous study of magnetic and electrocatalytic properties of cobaltites under extreme conditions expands the understanding of physical and chemical processes proceeding in them with the possibility of their further practical application. Therefore, La0.6Sr0.4CoO3 (LSCO) nanopowders were synthesized at different annealing temperatures tann = 850-900 °C, and their multifunctional properties were studied comprehensively. As tann increases, the rhombohedral perovskite structure of the LSCO becomes more single-phase, whereas the average particle size and dispersion grow. Co3+ and Co4+ are the major components. It has been found that LSCO-900 shows two main Curie temperatures, TC1 and TC2, associated with a particle size distribution. As pressure P increases, average ⟨TC1⟩ and ⟨TC2⟩ increase from 253 and 175 K under ambient pressure to 268 and 180 K under P = 0.8 GPa, respectively. The increment of ⟨dTC/dP⟩ for the smaller and bigger particles is sufficiently high and equals 10 and 13 K/GPa, respectively. The magnetocaloric effect in the LSCO-900 nanopowder demonstrates an extremely wide peak δTfwhm > 50 K that can be used as one of the composite components, expanding its working temperature window. Moreover, all LSCO samples showed excellent electrocatalytic performance for the oxygen evolution reaction (OER) process (overpotentials of only 265-285 mV at a current density of 10 mA cm-2) with minimal η10 for LSCO-900. Based on the experimental data, it was concluded that the formation of a dense amorphous layer on the surface of the particles ensures high stability as a catalyst (at least 24 h) during electrolysis in 1 M KOH electrolyte.
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Spin transition (ST) compounds have been extensively studied because of the changes in rich physicochemical properties accompanying the ST process. The study of ST mainly focuses on the temperature-induced spin transition (TIST). To further understand the ST, we explore the pressure response behavior of TIST and pressure-induced spin transition (PIST) of the 2D Hofmann-type ST compounds [Fe(Isoq)2M(CN)4] (Isoq-M) (M = Pt, Pd, Isoq = isoquinoline). The TISTs of both Isoq-Pt and Isoq-Pd compounds exhibit anomalous pressure response, where the transition temperature (T1/2) exhibits a nonlinear pressure dependence and the hysteresis width (ΔT1/2) exhibits a nonmonotonic behavior with pressure, by the synergistic influence of the intermolecular interaction and the distortion of the octahedral coordination environment. And the distortion of the octahedra under critical pressures may be the common behavior of 2D Hofmann-type ST compounds. Moreover, ΔT1/2 is increased compared with that before compression because of the partial irreversibility of structural distortion after decompression. At room temperature, both compounds exhibit completely reversible PIST. Because of the greater change in mechanical properties before and after ST, Isoq-Pt exhibits a more abrupt ST than Isoq-Pd. In addition, it is found that the hydrostatic properties of the pressure transfer medium (PTM) significantly affect the PIST due to their influence on spin-domain formation.
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Unlike the known aggregation-caused quenching (ACQ) that the enhancement of π-π interactions in rigid organic molecules usually decreases the luminescent emission, here we show that an intermolecular "head-to-head" π-π interaction in the phenanthrene crystal, forming the so-called "transannular effect", could result in a higher degree of electron delocalization and thus photoluminescent emission enhancement. Such a transannular effect is molecular configuration and stacking dependent, which is absent in the isomers of phenanthrene but can be realized again in the designed phenanthrene-based cocrystals. The transannular effect becomes more significant upon compression and causes anomalous piezoluminescent enhancement in the crystals. Our findings thus provide new insights into the effects of π-π interactions on luminescence emission and also offer new pathways for designing efficient aggregation-induced emission (AIE) materials to advance their applications.
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Interlayer coupling and stacking order play essential roles in shaping the exotic electronic properties of two-dimensional materials. Here, we employ restacked TaS2âa novel transition metal dichalcogenide (TMD) with weak vdW bonding and twisted anglesâto investigate the strain effects of interlayer modulation on the electronic properties. Under pressure, an unexpected transition from metallic to semiconducting-like states occurs. Superconductivity coexists with the semiconducting-like state over a wide pressure range, which has never before been observed in TMDs. Upon further compression, a new superconducting SC-II state emerges without structural evolution and gradually replaces the initial SC-I state. The emerging SC-II state exhibits robust zero-resistance superconductivity and an ultrahigh upper critical field. The abundant electronic state changes in RS-TaS2 are strongly related to band-structure engineering resulting from pressure-induced interlayer stacking angle modulation. Our results reveal the remarkable effect of interlayer rearrangement on electronic properties and provide a special way to explore the unique properties of 2D materials.
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The catalytic activity has been investigated in 2D materials, and the unique structural and electronic properties contribute to their success in conventional heterogeneous catalysis. Heterojunction-based piezocatalysis has attracted increasing attention due to the band-structure engineering and the enhanced charge carrier separation by prominent piezoelectric effect. However, the piezocatalytic behavior of van der Waals (vdW) heterostructures is still unknown, and the finite active sites, catalyst poisoning, and poor conductivity are challenges for developing good piezocatalysts. Herein, a reduced graphene oxide (rGO)-MoS2 heterostructure is rationally designed to tackle these challenges. The heterostructure shows a record-high piezocatalytic degradation rate of 1.40 × 102 L mol-1 s-1 , which is 7.86 times higher than MoS2 nanosheets. Piezoresponse force microscope measurements and density functional theory calculation reveal that the coupling between semiconductive and piezoelectric properties in the vdW heterojunction is vital to break the metallic state screening effect at the MoS2 edge for keeping the piezoelectric potential. The dynamic charges generated by MoS2 and the fast charge transfer in rGO activate and maintain catalytically active sites for pollutant degradation with an ultra-fast rate and good stability. The working mechanism opens new avenues for developing efficient catalysts significant to wastewater treatments and other applications.
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A novel piezo-activated luminescent material with wide range modulation of the luminescence wavelength and a giant intensity enhancement upon compression was prepared using a strategy of molecular doping. The doping of THT molecules into TCNB-perylene cocrystals results in the formation of a weak but pressure-enhanced emission center in the material at ambient pressure. Upon compression, the emissive band from the undoped component TCNB-perylene undergoes a normal red shift and emission quenching, while the weak emission center shows an anomalous blue shift from 615 nm to 574 nm and a giant luminescence enhancement up to 16 GPa. Further theoretical calculations show that doping by THT could modify intermolecular interactions, promote molecular deformation, and importantly, inject electrons into the host TCNB-perylene upon compression, which contributes to the novel piezochromic luminescence behavior. Based on this finding, we further propose a universal approach to design and regulate the piezo-activated luminescence of materials by using other similar dopants.
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Effective modification of the structure and properties of halide perovskites via the pressure engineering strategy has attracted enormous interest in the past decade. However, sufficient effort and insights regarding the potential properties and applications of the high-pressure amorphous phase are still lacking. Here, the superior and tunable photoelectric properties that occur in the pressure-induced amorphization process of the halide perovskite Cs3 Bi2 I9 are demonstrated. With increasing pressure, the photocurrent with xenon lamp illumination exhibits a rapid increase and achieves an almost five orders of magnitude increment compared to its initial value. Impressively, a broadband photoresponse from 520 to 1650 nm with an optimal responsivity of 6.81 mA W-1 and fast response times of 95/96 ms at 1650 nm is achieved upon successive compression. The high-gain, fast, broadband, and dramatically enhanced photoresponse properties of Cs3 Bi2 I9 are the result of comprehensive photoconductive and photothermoelectric mechanisms, which are associated with enhanced orbital coupling caused by an increase in BiI interactions in the [BiI6 ]3- cluster, even in the amorphous state. These findings provide new insights for further exploring the potential properties and applications of amorphous perovskites.
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Photoelectric devices based on the photothermoelectric (PTE) effect show promising prospects for broadband detection without an external power supply. However, effective strategies are still required to regulate the conversion efficiency of light to heat and electricity. Herein, significantly enhanced photoresponse properties of PbI2 generated from a PTE mechanism via a high-pressure strategy are reported. PbI2 exhibits a stable, fast, self-driven, and broadband photoresponse at ≈980 nm. Intriguingly, the synergy of the photoconductivity and PTE mechanism is conducive to enhancing the photoelectric properties, and extending the detection bandwidth to the optical communication waveband (1650 nm) with an external bias. The dramatically enhanced photoresponse characteristics are attributed to narrowing of the band gap and a significantly decreased resistance, which originate from the enhancement of atomic orbital overlap owing to pressure-induced Pb-I bond contraction. These findings open up a new avenue toward designing self-driven and broadband photoelectric devices.
RESUMEN
The emergence of superconductivity in two-dimensional (2D) materials has attracted tremendous research efforts because the origins and mechanisms behind the unexpected and fascinating superconducting phenomena remain unclear. In particular, the superconductivity can survive in 2D systems even with weakened disorder and broken spatial inversion symmetry. Here, structural and superconducting transitions of 2D van der Waals (vdW) hydrogenated germanene (GeH) are observed under compression and decompression processes. GeH possesses a superconducting transition with a critical temperature (Tc) of 5.41 K at 8.39 GPa. A crystalline to amorphous transition occurs at 16.80 GPa, while superconductivity remains. An abnormal increase of Tc up to 6.11 K was observed during the decompression process, while the GeH remained in the 2D amorphous phase. A combination study of in situ high-pressure synchrotron X-ray diffraction, in situ high-pressure Raman spectroscopy, transition electron microscopy, and density functional theory simulations suggests that the superconductivity in 2D vdW GeH is attributed to the increased density of states at the Fermi level as well as the enhanced electron-phonon coupling effect under high pressure even in the form of an amorphous phase. The unique pressure-induced phase transition of GeH from 2D crystalline to 2D amorphous metal hydride provides a promising platform to study the mechanisms of amorphous hydride superconductivity.
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Rare earth fluorides have been widely used in recent years in the field of solid-state lighting. However, the relationship between the structure and luminescence properties is still unclear. Herein, the photoluminescence and structural transition of CeF3:Tb3+ nanoparticles under high pressure were investigated through in situ photoluminescence and X-ray diffraction measurements. Intriguingly, the photoluminescence of CeF3:Tb3+ nanoparticles displays an enhancement from 18.3 to 33.4 GPa, accompanied by the phase transition from the starting hexagonal phase to the orthorhombic phase. It was found that the distance of luminescent centers increased sharply during the high-pressure phase transition, which weakened the quenching effect and improved transmission efficiency. Our work provides more insight into the optical characteristics and structures of rare earth trifluorides.
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Prospects for the use of manganites in various areas of modern technologies require comprehensive studies of their physical and chemical properties. La0.9Mn1.1O3 (LMO) ceramics have been synthesized at an annealing temperature tann of 1150 °C with further post-annealing at 1250, 1350, and 1450 °C. As tann increases, the structure symmetry changes, and both the crystallite size and chemical defects increase. The post-annealing, on one hand, leads to a dramatic reduction of the magnetocaloric effect (MCE) |-ΔSmaxM| from 3.50 to 0.75 J (kg K)-1 at 2 T and a Curie temperature TC from 227 to 113 K with increasing tann. On the other hand, an external hydrostatic high-pressure P works oppositely enhancing ferromagnetic interactions. The saturation of -ΔSmaxM and TC is already achieved at a relatively low P of ≈ 0.4 GPa. LMO-1150 exhibits the best magnetocaloric characteristics compared with other studied samples. Moreover, the electrochemical characteristics of the LMO materials as electrocatalysts for overall water splitting (OER process) and features of their transformation in different 0.5 M K2SO4, 0.5 M K2HPO4, and 0.1 M K2B4O7 electrolytes have been studied thoroughly. After electrocatalysis of LMO, the magnetization M decreases and TC remains, which makes it possible to control the depletion of electrodes and predict their working time based on the magnetic measurements. All samples show the best OER activity in the 0.5 M K2HPO4 media. The obtained results demonstrate the ways for controlling the MCE of LMO under changing internal and external conditions, and an evaluation of the possibilities for their OER applications in electrocatalysts.
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Recently, the possibility of exploiting the phenomenon of spin transition (ST) has been intensively investigated; therefore, it is particularly important to study the behavior of ST under various stimuli. Here, the shape and content of the intermediate phase of ST in Hoffmann-like compounds [Fe(Fpz)2M(CN)4] (M = Pt, Pd) under external stimuli are studied. For this purpose, magnetic and Raman spectroscopy studies were carried out. In pressure-induced spin transition (PIST), a mixture of high-spin and low-spin states appears, while in temperature-induced spin transition (TIST), a homogeneous state occurs. The first-order ST induced by pressure has a hysteresis but is not abrupt. However, the temperature-induced spin transition at ambient pressure is hysteretic and abrupt. To investigate this difference, we discuss using a thermodynamic model that considers elastic interactions, showing that the slope of the hysteresis loop is related to the appearance of internal pressure, which is related to the difference in sample compressibility under high-spin and low-spin states.
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Exploring the behavior of nanocrystals with varying shapes and sizes under high pressure is crucial to understanding the relationship between the morphology and properties of nanomaterials. In this study, we investigated the compression behaviors of WS2 nanotubes (NT-WS2) and fullerene-like nanoparticles (IF-WS2) by in situ high-pressure X-ray diffraction (XRD) and Raman spectroscopy. It was found that the bulk modulus of NT-WS2 is 81.7 GPa, which is approximately twice as large as that of IF-WS2 (46.3 GPa). This might be attributed to the fact that IF-WS2 with larger d-spacing along the c-axis and higher defect density are more compressible under isotropic pressure than NT-WS2. Thus, the slender NT-WS2 possess a more stable crystal structure than the IF-WS2. Our findings reveal that the effects of morphology and size play crucial roles in determining the high-pressure properties of WS2 nanoparticles, and provide significant insight into the relationship between structure and properties.
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Lead-free halide double perovskites (DPs) have been proposed as stable and promising alternatives to lead halide perovskites. Understanding the structural-optical properties of halide DPs is important for their applications. In this study, Cs2AgInCl6 DP nanocrystals, with a direct band gap, were synthesized and studied. Because of a strong electron-phonon coupling leading to exciton self-trapping, a broad emission with a large Stokes shift of Cs2AgInCl6 DP nanocrystals is observed. We observed an abnormal blue-shifted emission accompanied by a red-shifted direct absorption edge because of the reduced electron-phonon coupling under compression in the cubic phase Cs2AgInCl6 DP nanocrystals. Our study clarified the basic structural-optical correlation of halide DPs and may promote their application in related fields.
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Pressure has always been an effective method for uncovering novel phenomena and properties in condensed matter physics. Here, an electrical transport study is carried on 2H-TaS2 up to ≈208 GPa, and an unexpected superconducting state (SC-II) emerging around 86.1 GPa with an initial critical temperature (Tc ) of 9.6 K is found. As pressure increases, the Tc enhances rapidly and reaches a maximum of 16.4 K at 157.4 GPa, which sets a new record for transition metal dichalcogenides (TMDs). The original superconducting state (SC-I) is found to be re-enhanced above 100 GPa after the recession around 10 GPa, and coexists with SC-II to the highest pressure applied in this work. In situ high-pressure X-ray diffraction and Hall effect measurements reveal that the occurrence of SC-II is accompanied by a structural modification and a concurrent enhancement of hole carrier density. The new high-Tc superconducting state in 2H-TaS2 can be attributed to the change of the electronic states near the Fermi surface, owing to pressure-induced interlayer modulation. It is the first time finding this remarkable superconducting state in TMDs, which not only brings a new broad of perspective on layered materials but also expands the field of pressure-modified superconductivity.
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Amorphous materials inherit short- and medium-range order from the corresponding crystal and thus preserve some of its properties while still exhibiting novel properties1,2. Due to its important applications in technology, amorphous carbon with sp2 or mixed sp2-sp3 hybridization has been explored and prepared3,4, but synthesis of bulk amorphous carbon with sp3 concentration close to 100% remains a challenge. Such materials inherit the short-/medium-range order of diamond and should also inherit its superior properties5. Here, we successfully synthesized millimetre-sized samples-with volumes 103-104 times as large as produced in earlier studies-of transparent, nearly pure sp3 amorphous carbon by heating fullerenes at pressures close to the cage collapse boundary. The material synthesized consists of many randomly oriented clusters with diamond-like short-/medium-range order and possesses the highest hardness (101.9 ± 2.3 GPa), elastic modulus (1,182 ± 40 GPa) and thermal conductivity (26.0 ± 1.3 W m-1 K-1) observed in any known amorphous material. It also exhibits optical bandgaps tunable from 1.85 eV to 2.79 eV. These discoveries contribute to our knowledge about advanced amorphous materials and the synthesis of bulk amorphous materials by high-pressure and high-temperature techniques and may enable new applications for amorphous solids.