Conventional Tb^(3+)-doped phosphors typically suffer from concentration quenching once the doping level exceeds a critical threshold.Consequently,the development of Tb^(3+)phosphors with intrinsic resistance to conce...Conventional Tb^(3+)-doped phosphors typically suffer from concentration quenching once the doping level exceeds a critical threshold.Consequently,the development of Tb^(3+)phosphors with intrinsic resistance to concentration quenching has become a key research focus.In this work,we successfully synthesized KBi(MoO_(4))_(2):x Tb^(3+)(x=0-100 at%)(denoted as KBM:x Tb^(3+))phosphors via a high-temperature solid-state reaction.Remarkably,no concentration quenching was observed across the entire doping range.This anti-quenching behavior originates from the large Tb^(3+)-Tb^(3+)interionic distance(>5Å)inherent to the quasi-layered crystal structure,which effectively suppresses multipole-interaction-mediated energy migration.At full Tb^(3+)substitution(x=100 at%),the material undergoes a structural phase transition from the monoclinic KBM phase to the triclinicα-KTb(MoO_(4))_(2)(α-KTM)phase.Theα-KTM phosphor exhibits excellent thermal stability(activation energy=0.6129 eV)and a single-exponential decay profile,whereas KBM:x Tb^(3+)(x<100%)display double-exponential decay behaviors,attributed to dual energy transfer pathways.These findings provide new insights into the luminescence mechanisms of high-concentration rare-earth-doped systems and offer guidance for designing nextgeneration anti-quenching phosphors.展开更多
LiFePO_(4)has normal olivine-structured(a-LFP)and high pressure(b-LFP)phases,with the former being one of the cathode materials for commercial Li-ion batteries.Despite extensive focus on the respective electrochemical...LiFePO_(4)has normal olivine-structured(a-LFP)and high pressure(b-LFP)phases,with the former being one of the cathode materials for commercial Li-ion batteries.Despite extensive focus on the respective electrochemical properties of the two phases,there is a lack of comparative studies on their electronic and magnetic properties,and the origin of the structural phase transition remains unclear.By combining first-principles calculations with molecular dynamics simulations,we find that the anisotropic compression of Li-O bonds drives the structural phase transition from a-LFP to b-LFP at a critical pressure of 20 GPa,while b-LFP undergoes a transition from semiconductor to metal due to Fe^(3+)generated during delithiation.Their antiferromagnetic(AFM)ground states are predicted to arise from the negative magnetic exchange interactions between nearest and next-nearest neighbor sites,with the corresponding N'eel temperature showing significant enhancement under pressure.Furthermore,compared with a-LFP,b-LFP shows increases in bulk,shear,and Young’s moduli of 8%,13%,and 12%,respectively.These findings enrich the physical property data of LiFePO_(4)phase compounds,providing knowledge for expanding the application scenarios of the a-LFP phase under special operating conditions such as high pressure.展开更多
The pressure-induced structural transitions of ZnTe are investigated at pressures up to 59.2 GPa in a diamond anvil cell by using synchrotron powder x-ray diffraction method. A phase transition from the initial zinc b...The pressure-induced structural transitions of ZnTe are investigated at pressures up to 59.2 GPa in a diamond anvil cell by using synchrotron powder x-ray diffraction method. A phase transition from the initial zinc blende （ZB, ZnTe-Ⅰ） structure to a cinnabar phase （ZnTe-Ⅱ） is observed at 9.6 GPa, followed by a high pressure orthorhombic phase （ZnTe-Ⅲ） with Cmcm symmetry at 12.1 GPa. The ZB, cinnabar （space group P3121）, Cmcm, P31 and rock salt structures of ZnTe are investigated by using density functional theory calculations. Based on the experiments and calculations, the ZnTe-Ⅱ phase is determined to have a cinnabar structure rather than a P3 1 symmetry.展开更多
We report a comprehensive study on a layered-structure compound of NaZn_(4)As_(3),which has been predicted to be an ideal topological semimetal(TSM) candidate.It is found that NaZn_(4)As_(3) undergoes a structural tra...We report a comprehensive study on a layered-structure compound of NaZn_(4)As_(3),which has been predicted to be an ideal topological semimetal(TSM) candidate.It is found that NaZn_(4)As_(3) undergoes a structural transformation from high temperature rhombohedral to a low temperature monoclinic phase.The electric resistivity exhibits a metal-to-insulatorlike transition at around 100 K,and then develops a plateau at low temperature,which might be related to the protected topologically conducting surface states.Our first-principles calculation confirms further that NaZn_(4)As_(3) is a topological insulator(TI) for both different phases rather than a previously proposed TSM.The Hall resistivity reveals that the hole carriers dominate the transport properties for the whole temperature range investigated.Furthermore,an obvious kink possibly associated to the structure transition has been detected in thermopower around ~ 170 K.The large thermopower and moderate κ indicate that NaZn_(4)As_(3) and/or its derivatives can provide a good platform for optimizing and studying the thermoelectric performance.展开更多
The interplay between superconductivity and structural phase transition has attracted enormous interest in recent years. For example, in Fe-pnictide high temperature superconductors, quantum fluctuations in associatio...The interplay between superconductivity and structural phase transition has attracted enormous interest in recent years. For example, in Fe-pnictide high temperature superconductors, quantum fluctuations in association with structural phase transition have been proposed to lead to many novel physical properties and even the superconductivity itself. Here we report a finding that the quasi-skutterudite superconductors （Sr1-xCax）3Ir4Sn13 （x = 0, 0.5, 1） and Ca3Rh4Snl3 show some unusual properties similar to the Fe-pnictides, through 119Sn nuclear magnetic resonance （NMR） measurements. In （Sr1-xCax）3Ir4Sn13, the NMR linewidth increases below a temperature T＊ that is higher than the structural phase transition temperature Ts. The spin-lattice relaxation rate （1/T1 ） divided by temperature （T）, 1/TI T and the Knight shift K increase with decreasing T down to T＊, but start to decrease below T＊, and followed by more distinct changes at Ts. In contrast, none of the anomalies is observed in Ca3Rh4Sn13 that does not undergo a structural phase transition. The precursory phenomenon above the structural phase transition resembles that occurring in Fe-pnictides. In the superconducting state of Ca3Ir4Sn13, 1/T1 decays as exp（-△/kBT） with a large gap △ = 2.21kBTc, yet without a Hebel-Slichter coherence peak, which indicates strong-coupling superconductivity. Our results provide new insight into the relationship between superconductivity and the electronic-structure change associated with structural phase transition.展开更多
We investigate the electronic structures and phase stability of ZnO, CdO and the related alloys in rocksalt（B1）and wurzite（B4） crystal, using the first-principle density functional theory within the hybrid functio...We investigate the electronic structures and phase stability of ZnO, CdO and the related alloys in rocksalt（B1）and wurzite（B4） crystal, using the first-principle density functional theory within the hybrid functional approximation. By varying the concentration of Zn components from 0% to 100%, we find that the Zn_xCd（1-x）O alloy undergoes a phase transition from octahedron to tetrahedron at x = 0.32, in agreement with the recent experimental findings. The phase transition leads to a mutation of the electron mobility originated from the changes of the effective mass. Our results qualify Zn O/Cd O alloy as an attractive candidate for photo-electrochemical and solar cell power applications.展开更多
Using DTA (difFerential thermal analysis) measurement on nanostructured TiO2, we find two endothermic peaks on the DTA curve. From XRD (X-ray diffraction) analysis of the original nanostructured TiO2 and its heat-trea...Using DTA (difFerential thermal analysis) measurement on nanostructured TiO2, we find two endothermic peaks on the DTA curve. From XRD (X-ray diffraction) analysis of the original nanostructured TiO2 and its heat-treated samples, we obtain the following results: the first endothermic peak corresponds to the desorption of physical or chemical absorption, the second one is related to the structural phase transition from brookite to anatase then to rutile, and this structural phase transition is beneficial to the grain growth of nanocrystal展开更多
The doping of the spinel ferrites with selective cations usually improves the properties of the parent ferrite.The effect of Co^(2+)/Gd^(3+)co-substitution on the microstructure,optical,and magnetic properties of Cu1-...The doping of the spinel ferrites with selective cations usually improves the properties of the parent ferrite.The effect of Co^(2+)/Gd^(3+)co-substitution on the microstructure,optical,and magnetic properties of Cu1-xCoxFe2-xGdxO4 prepared by the citrate-nitrate auto-combustion synthesis was investigated.Characterization of the samples was performed with powder X-ray diffraction(XRD),Raman and Fouriertransform infrared(FTIR)spectroscopy,field-emission scanning electron microscopy,X-ray energydispersive spectroscopy,UV-Vis spectroscopy,and a vibrating sample magnetometer.The results of XRD,Raman,and FTIR analysis show a gradual structural phase transition from a tetragonal(I41/amd)structure to a cubic(Fd3m)structure.The bandgap energy of the studied samples is in a range of 1.57-1.75 eV with a minimum in sample x=0.06 and then increases.Magnetic investigations show that the presence of Co^(2+)/Gd^(3+)cations in an octahedral site of the copper ferrite structure could increase saturation magnetization and coercive field from 567.9 Oe and 23.62 emu/g to 929.4 Oe and 28.27 emu/g,respectively.展开更多
Organic-inorganic metal halides(OIMHs)possessing switchable optical and electrical properties hold significant promise for applications in multifunctional sensors,switching devices,and information storage.However,the ...Organic-inorganic metal halides(OIMHs)possessing switchable optical and electrical properties hold significant promise for applications in multifunctional sensors,switching devices,and information storage.However,the challenge lies in achieving effective regulation of optical/electric responses through structural design strategies,and materials with structural phase transition coupling photoluminescence(PL)quenching are also relatively rare.Here,by employing halogen engineering to modify the parent compound(TEMA)PbBr_(3)(TEMA=triethylmethylammonium),we successfully obtained two derivatives(TECA)PbBr_(3) and(TEBA)PbBr_(3)(TECA=triethylchloromethylammonium and TEBA=triethylbromomethylammonium).Halogen engineering successfully introduces halogen-halogen interactions between PbBr_(3) n-inorganic frameworks and organic cations,which increases the stretching distortion of the PbBr_(6) octahedral framework of(TECA)PbBr_(3) and(TEBA)PbBr_(3),accompanied by prominent orange-red broadband emission behavior in(TECA)PbBr_(3) and(TEBA)PbBr_(3).Meanwhile,the phase transition temperatures(Tp)of(TECA)PbBr_(3) and(TEBA)PbBr_(3) have also been significantly increased compared to(TEMA)PbBr_(3),and two derivatives demonstrated switchable dielectric responses.Impressively,the reversible structural phase transition of(TECA)PbBr_(3) and(TEBA)PbBr_(3) dominates the outright PL quenching behavior,while still maintaining high PL emission intensity below the Tp.This represents a rare and extraordinary phenomenon in the realm of bistable responsive materials.This work provides a feasible strategy for designing and modulating photoluminescent phase transition materials and deepens understanding of the structural-performance relationship.展开更多
Three-dimensional anion frameworks loaded with small cationic molecules are often reasonable models for the design of switching materials.However,due to limitations of the bond length and structural stability,it is di...Three-dimensional anion frameworks loaded with small cationic molecules are often reasonable models for the design of switching materials.However,due to limitations of the bond length and structural stability,it is difficult for the framework to carry larger molecules,so it is still a challenge to construct frameworks with larger capacities.展开更多
Organic-inorganic hybrids have shown great potential for assembling dielectric phase transition materials,due to their unique characteristics and structural diversities.Here,we construct a new organic-organic hybrid,(...Organic-inorganic hybrids have shown great potential for assembling dielectric phase transition materials,due to their unique characteristics and structural diversities.Here,we construct a new organic-organic hybrid,(cyclopropylaminium)_(3)BiBr_(6)(1),which consists of a zero-dimensional inorganic framework of BiBr_(6)octahedra and ternary cyclic organic cations.展开更多
Surface depletion field would introduce the depletion region near surface and thus could significantly alter the optical,electronic and optoelectronic properties of the materials,especially low-dimensional materials.T...Surface depletion field would introduce the depletion region near surface and thus could significantly alter the optical,electronic and optoelectronic properties of the materials,especially low-dimensional materials.Two-dimensional(2D)organic—inorganic hybrid perovskites with van der Waals bonds in the out-of-plane direction are expected to have less influence from the surface depletion field;nevertheless,studies on this remain elusive.Here we report on how the surface depletion field affects the structural phase transition,quantum confinement and Stark effect in 2D(BA)2PbI4 perovskite microplates by the thickness-,temperature-and power-dependent photoluminescence(PL)spectroscopy.Power dependent PL studies suggest that high-temperature phase(HTP)and low-temperature phase(LTP)can coexist in a wider temperature range depending on the thickness of the 2D perovskite microplates.With the decrease of the microplate thickness,the structural phase transition temperature first gradually decreases and then increases below 25 nm,in striking contrast to the conventional size dependent structural phase transition.Based on the thickness evolution of the emission peaks for both high-temperature phase and low-temperature phase,the anomalous size dependent phase transition could probably be ascribed to the surface depletion field and the surface energy difference between polymorphs.This explanation was further supported by the temperature dependent PL studies of the suspended microplates and encapsulated microplates with graphene and boron nitride flakes.Along with the thickness dependent phase transition,the emission energies of free excitons for both HTP and LTP with thickness can be ascribed to the surface depletion induced confinement and Stark effect.展开更多
The engineering of switchable materials with controllable stimuli-responsive multistability remains challenging in materials science.Herein,we present syntheses and structural and magnetic studies of a one-dimensional...The engineering of switchable materials with controllable stimuli-responsive multistability remains challenging in materials science.Herein,we present syntheses and structural and magnetic studies of a one-dimensional cobalt(Ⅱ)coordination polymer[(enbzp)Co(bpy)](ClO_(4))_(2)·-MeOH·H2O(1;enbzp=N,N′-(ethane-1,2-diyl)bis(1-phenyl-1-(pyridin-2-yl)methanimine,bpy=4,4′-bipyridine)and its desolvated analogue[(enbzp)Co(bpy)](ClO_(4))_(2)(2),obtained by reversible single-crystal-to-single-crystal(SCSC)transformation.展开更多
We report^(75) As nuclear magnetic resonance(NMR)/nuclear quadrupole resonance(NQR) and transmission electron microscopy(TEM) studies on LaFeAsO_(1-x)F_x. There are two superconducting domes in this material. The firs...We report^(75) As nuclear magnetic resonance(NMR)/nuclear quadrupole resonance(NQR) and transmission electron microscopy(TEM) studies on LaFeAsO_(1-x)F_x. There are two superconducting domes in this material. The first one appears at 0.03 ≤ x ≤0.2 with T_c^(max) = 27 K, and the second one at 0.25 ≤x≤0.75 with T_c^(max) = 30 K. By NMR and TEM, we demonstrate that a C4-to-C2 structural phase transition(SPT) takes place above both domes, with the transition temperature T_s varying strongly with x. In the first dome, the SPT is followed by an antiferromagnetic(AF) transition, but neither AF order nor low-energy spin fluctuations are found in the second dome. By ^(75) As nuclear spin-lattice relaxation rate(1/T_1) measurements, we find that AF order and superconductivity coexist microscopically in LaFeAsO_(0.97) F_(0.03). In the coexisting region, 1/T_1 decreases at T_c but becomes proportional to T below 0.6 T_c, indicating gapless excitations. Therefore, in contrast to the early reports, the obtained phase diagram for x ≤ 0.2 is quite similar to the doped BaFe_2As_2 system. The electrical resistivity p in the second dome can be fitted by ρ = ρ0 + AT^n with n = 1 and a maximal coefficient A at around xopt = 0.5-0.55 at which T_s extrapolates to zero and Tc is the maximal, which suggests the importance of quantum critical fluctuations associated with the SPT. We have constructed a complete phase diagram of LaFeAsO_(1-x)F_x, which provides insight into the relationship between SPT, antiferromagnetism and superconductivity.展开更多
In the realm of molecular phase transition research,particularly for applications in sensors,data storage and switching technologies,the role of organic-inorganic hybrid perovskite materials has been increasingly reco...In the realm of molecular phase transition research,particularly for applications in sensors,data storage and switching technologies,the role of organic-inorganic hybrid perovskite materials has been increasingly recognized for their significant potential.Nevertheless,hybrid post-perovskites,as a critical subclass of perovskites,have not been thoroughly studied and mainly limit in the instances based on polyatomic bridging agents like dicyanamide(dca^(-))and non-cyclic organic cations.Herein,a polar cyclic quaternary ammonium cation,N,N-dimethylpyrrolidinium(DMP^(+)),was used to assemble a new hybrid post-perovskite,(DMP)[Mn(dca)_(3)](1),which undergoes a phase transition from orthorhombic Bmmb to monoclinic P2_(1)/n space group at 249 K.By employing multiple techniques such as differential scanning calorimetry,variable-temperature single-crystal X-ray analysis,dielectric measurements,and Hirshfeld surface analysis,we disclosed the role of polar cyclic quaternary ammonium DMP^(+)in elevating the phase-transition temperature by 48 K,generating significant dielectric switching effect and facilitating interlayer sliding of inorganic framework.展开更多
The structural, electronic and mechanical properties of transition metal hydrides （TMH, TM=Mo, Tc, Ru） are investigated by means of first principles calculation based on density fimctional theory with generalized gr...The structural, electronic and mechanical properties of transition metal hydrides （TMH, TM=Mo, Tc, Ru） are investigated by means of first principles calculation based on density fimctional theory with generalized gradient approximation. Among the five crystallographic structures that have been investigated, the cubic phase is found to be more stable than the hexagonal ones. A structural phase transition from ZB to WC in Moll, NaC1 to NiAs in TcH and NaCI to ZB to NiAs in RuH is also predicted under high pressure. The calculated elastic constants indicate that all the three hydrides are mechanically stable at ambient pressure.展开更多
The hybridization between the localized 4f level(f) with conduction(c) electrons in γ-Ce upon cooling has been previously revealed in single crystalline thin films experimentally and theoretically, whereas its influe...The hybridization between the localized 4f level(f) with conduction(c) electrons in γ-Ce upon cooling has been previously revealed in single crystalline thin films experimentally and theoretically, whereas its influence on the γ → α phase transition was not explicitly verified, due to the fact that the phase transition happened in the bulk-layer, leaving the surface in the γ phase. Here in our work, we circumvent this issue by investigating the effect of alloying addition of La on Ce, by means of crystal structure, electronic transport and angle resolved photoemission spectroscopy measurements, together with a phenomenological periodic Anderson model and a modified Anderson impurity model. Our current researches indicate that the weakening of f–c hybridization is the major factor in the suppression of γ → α phase transition by La doping. The consistency of our results with the effects of other rare earth and actinide alloying additions on the γ → α phase transition of Ce is also discussed. Our work demonstrates the importance of the interaction between f and c electrons in understanding the unconventional phase transition in Ce, which is intuitive for further researches on other rare earth and actinide metals and alloys with similar phase transition behaviors.展开更多
A novel inorganic-organic hybrid supramolecular compound,[（3-nitroanilinium^＋）（18-crown-6）][IO4]（CH3OH）（1）,was discovered as phase-transition materials displaying dielectric anomalous behaviors.The yellow blo...A novel inorganic-organic hybrid supramolecular compound,[（3-nitroanilinium^＋）（18-crown-6）][IO4]（CH3OH）（1）,was discovered as phase-transition materials displaying dielectric anomalous behaviors.The yellow block crystal formed by N-H…O hydrogen bonding that made contact through the cavity of 18-crown-6 was characterized by single-crystal X-ray diffraction,elemental analysis,infrared analysis,thermogravimetric analysis,differential scanning calorimetry,and potential-energy calculations.Differential scanning calorimetry measurements indicate that the compound experiences a reversible phase transition at around 220 K.Temperature-dependent dielectric measurements further confirm the phase transitions.Potential-energy calculations demonstrate that the phase transition occurs due to the molecular order-disorder rotation of CH3OH,whereas the space grouping of the crystal remains unchanged.展开更多
A new phase transition compound,2-methoxyanilinium perchlorate-18-crown-6（1） {（oCH3OC6H4NH3）＋（18-crown-6） ClO4 },has been synthesized and separated as crystals.Differential scanning calorimetry（DSC） measureme...A new phase transition compound,2-methoxyanilinium perchlorate-18-crown-6（1） {（oCH3OC6H4NH3）＋（18-crown-6） ClO4 },has been synthesized and separated as crystals.Differential scanning calorimetry（DSC） measurements show a pair of sharp peaks at 225 K（heating） and 210 K（cooling）,indicating the phase transition is first-order.Dielectric anomalies observed at 225 K（heating）and 210 K（cooling） further confirm the phase transition.The crystal structures determined at 298 K and123 K are both triclinic in P 1.The most distinct difference between room-temperature and lowtemperature structures is the order–disorder transition of the host 18-crown-6 molecule,which is the driving force of the phase transition.展开更多
The atomic geometry, structure stability, electronic and magnetic properties of VSe2 were systematically investigated based on the density functional theory（DFT）. Varying from 3D to 2D four VSe2 structures, bulk 2H-...The atomic geometry, structure stability, electronic and magnetic properties of VSe2 were systematically investigated based on the density functional theory（DFT）. Varying from 3D to 2D four VSe2 structures, bulk 2H-VSe2 and 1T-VSe2, monolayer H-VSe2 and T-VSe2 are all demonstrated as thermodynamically stable by lattice dynamic calculations. More interestingly, the phase transition temperature is dramatically different due to the lattice size. Finally, owing to different crystal structures, H-VSe2 is semimetallic whereas T-VSe2 is totally metallic and also they have different magnetic moments. Our main argument is that being exfoliated from bulk to monolayer, 2H-VSe2 transforms to T-VSe2, accompanied by both semimetallic-metallic transition and dramatic magnetic moment variation. Our calculations provide a novel structure phase transition and an efficient way to modulate the electronic structure and magnetic moment of layered VSe2, which suggests potential applications as high-performance functional nanomaterial.展开更多
基金supported by the Natural Science Research Project of Anhui Province Education Department for Excellent Young Scholars(Grant No.2024AH030007)the National Natural Science Foundation of China(Grant No.52202001)。
文摘Conventional Tb^(3+)-doped phosphors typically suffer from concentration quenching once the doping level exceeds a critical threshold.Consequently,the development of Tb^(3+)phosphors with intrinsic resistance to concentration quenching has become a key research focus.In this work,we successfully synthesized KBi(MoO_(4))_(2):x Tb^(3+)(x=0-100 at%)(denoted as KBM:x Tb^(3+))phosphors via a high-temperature solid-state reaction.Remarkably,no concentration quenching was observed across the entire doping range.This anti-quenching behavior originates from the large Tb^(3+)-Tb^(3+)interionic distance(>5Å)inherent to the quasi-layered crystal structure,which effectively suppresses multipole-interaction-mediated energy migration.At full Tb^(3+)substitution(x=100 at%),the material undergoes a structural phase transition from the monoclinic KBM phase to the triclinicα-KTb(MoO_(4))_(2)(α-KTM)phase.Theα-KTM phosphor exhibits excellent thermal stability(activation energy=0.6129 eV)and a single-exponential decay profile,whereas KBM:x Tb^(3+)(x<100%)display double-exponential decay behaviors,attributed to dual energy transfer pathways.These findings provide new insights into the luminescence mechanisms of high-concentration rare-earth-doped systems and offer guidance for designing nextgeneration anti-quenching phosphors.
基金supported by the National Natural Science Foundation of China(Grant No.12304089)the start-up foundation from Shanghai University。
文摘LiFePO_(4)has normal olivine-structured(a-LFP)and high pressure(b-LFP)phases,with the former being one of the cathode materials for commercial Li-ion batteries.Despite extensive focus on the respective electrochemical properties of the two phases,there is a lack of comparative studies on their electronic and magnetic properties,and the origin of the structural phase transition remains unclear.By combining first-principles calculations with molecular dynamics simulations,we find that the anisotropic compression of Li-O bonds drives the structural phase transition from a-LFP to b-LFP at a critical pressure of 20 GPa,while b-LFP undergoes a transition from semiconductor to metal due to Fe^(3+)generated during delithiation.Their antiferromagnetic(AFM)ground states are predicted to arise from the negative magnetic exchange interactions between nearest and next-nearest neighbor sites,with the corresponding N'eel temperature showing significant enhancement under pressure.Furthermore,compared with a-LFP,b-LFP shows increases in bulk,shear,and Young’s moduli of 8%,13%,and 12%,respectively.These findings enrich the physical property data of LiFePO_(4)phase compounds,providing knowledge for expanding the application scenarios of the a-LFP phase under special operating conditions such as high pressure.
基金Supported by the National Natural Science Foundation of China under Grant No 11474280the National Basic Research Program of China under Grant No 2011CB808200the Chinese Academy of Sciences under Grant Nos KJCX2-SW-N20 and KJCX2-SW-N03
文摘The pressure-induced structural transitions of ZnTe are investigated at pressures up to 59.2 GPa in a diamond anvil cell by using synchrotron powder x-ray diffraction method. A phase transition from the initial zinc blende （ZB, ZnTe-Ⅰ） structure to a cinnabar phase （ZnTe-Ⅱ） is observed at 9.6 GPa, followed by a high pressure orthorhombic phase （ZnTe-Ⅲ） with Cmcm symmetry at 12.1 GPa. The ZB, cinnabar （space group P3121）, Cmcm, P31 and rock salt structures of ZnTe are investigated by using density functional theory calculations. Based on the experiments and calculations, the ZnTe-Ⅱ phase is determined to have a cinnabar structure rather than a P3 1 symmetry.
基金Project supported by the National Natural Science Foundation of China (Grant Nos. 11874417 and 12274440)the Strategic Priority Research Program (B) of Chinese Academy of Sciences (Grant No. XDB33010100)the Fund from the Ministry of Science and Technology of China (Grant No. 2022YFA1403903)。
文摘We report a comprehensive study on a layered-structure compound of NaZn_(4)As_(3),which has been predicted to be an ideal topological semimetal(TSM) candidate.It is found that NaZn_(4)As_(3) undergoes a structural transformation from high temperature rhombohedral to a low temperature monoclinic phase.The electric resistivity exhibits a metal-to-insulatorlike transition at around 100 K,and then develops a plateau at low temperature,which might be related to the protected topologically conducting surface states.Our first-principles calculation confirms further that NaZn_(4)As_(3) is a topological insulator(TI) for both different phases rather than a previously proposed TSM.The Hall resistivity reveals that the hole carriers dominate the transport properties for the whole temperature range investigated.Furthermore,an obvious kink possibly associated to the structure transition has been detected in thermopower around ~ 170 K.The large thermopower and moderate κ indicate that NaZn_(4)As_(3) and/or its derivatives can provide a good platform for optimizing and studying the thermoelectric performance.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11674377 and 11634015)the National Key R&D Program of China(Grant Nos.2017YFA0302904 and 2016YFA0300502)+1 种基金the Strategic Priority Research Program(B)of the Chinese Academy of Sciences(Grant No.XDB07020200)supported by the Youth Innovation Promotion Association of CAS
文摘The interplay between superconductivity and structural phase transition has attracted enormous interest in recent years. For example, in Fe-pnictide high temperature superconductors, quantum fluctuations in association with structural phase transition have been proposed to lead to many novel physical properties and even the superconductivity itself. Here we report a finding that the quasi-skutterudite superconductors （Sr1-xCax）3Ir4Sn13 （x = 0, 0.5, 1） and Ca3Rh4Snl3 show some unusual properties similar to the Fe-pnictides, through 119Sn nuclear magnetic resonance （NMR） measurements. In （Sr1-xCax）3Ir4Sn13, the NMR linewidth increases below a temperature T＊ that is higher than the structural phase transition temperature Ts. The spin-lattice relaxation rate （1/T1 ） divided by temperature （T）, 1/TI T and the Knight shift K increase with decreasing T down to T＊, but start to decrease below T＊, and followed by more distinct changes at Ts. In contrast, none of the anomalies is observed in Ca3Rh4Sn13 that does not undergo a structural phase transition. The precursory phenomenon above the structural phase transition resembles that occurring in Fe-pnictides. In the superconducting state of Ca3Ir4Sn13, 1/T1 decays as exp（-△/kBT） with a large gap △ = 2.21kBTc, yet without a Hebel-Slichter coherence peak, which indicates strong-coupling superconductivity. Our results provide new insight into the relationship between superconductivity and the electronic-structure change associated with structural phase transition.
基金Supported by the National Natural Science Foundation of China under Grant Nos 11474273 and 11634003the Youth Innovation Promotion Association of Chinese Academy of Sciences under Grant No 2017154
文摘We investigate the electronic structures and phase stability of ZnO, CdO and the related alloys in rocksalt（B1）and wurzite（B4） crystal, using the first-principle density functional theory within the hybrid functional approximation. By varying the concentration of Zn components from 0% to 100%, we find that the Zn_xCd（1-x）O alloy undergoes a phase transition from octahedron to tetrahedron at x = 0.32, in agreement with the recent experimental findings. The phase transition leads to a mutation of the electron mobility originated from the changes of the effective mass. Our results qualify Zn O/Cd O alloy as an attractive candidate for photo-electrochemical and solar cell power applications.
文摘Using DTA (difFerential thermal analysis) measurement on nanostructured TiO2, we find two endothermic peaks on the DTA curve. From XRD (X-ray diffraction) analysis of the original nanostructured TiO2 and its heat-treated samples, we obtain the following results: the first endothermic peak corresponds to the desorption of physical or chemical absorption, the second one is related to the structural phase transition from brookite to anatase then to rutile, and this structural phase transition is beneficial to the grain growth of nanocrystal
文摘The doping of the spinel ferrites with selective cations usually improves the properties of the parent ferrite.The effect of Co^(2+)/Gd^(3+)co-substitution on the microstructure,optical,and magnetic properties of Cu1-xCoxFe2-xGdxO4 prepared by the citrate-nitrate auto-combustion synthesis was investigated.Characterization of the samples was performed with powder X-ray diffraction(XRD),Raman and Fouriertransform infrared(FTIR)spectroscopy,field-emission scanning electron microscopy,X-ray energydispersive spectroscopy,UV-Vis spectroscopy,and a vibrating sample magnetometer.The results of XRD,Raman,and FTIR analysis show a gradual structural phase transition from a tetragonal(I41/amd)structure to a cubic(Fd3m)structure.The bandgap energy of the studied samples is in a range of 1.57-1.75 eV with a minimum in sample x=0.06 and then increases.Magnetic investigations show that the presence of Co^(2+)/Gd^(3+)cations in an octahedral site of the copper ferrite structure could increase saturation magnetization and coercive field from 567.9 Oe and 23.62 emu/g to 929.4 Oe and 28.27 emu/g,respectively.
基金supported by the National Natural Science Foundation of China(Grant No.21991141 and 22371258)。
文摘Organic-inorganic metal halides(OIMHs)possessing switchable optical and electrical properties hold significant promise for applications in multifunctional sensors,switching devices,and information storage.However,the challenge lies in achieving effective regulation of optical/electric responses through structural design strategies,and materials with structural phase transition coupling photoluminescence(PL)quenching are also relatively rare.Here,by employing halogen engineering to modify the parent compound(TEMA)PbBr_(3)(TEMA=triethylmethylammonium),we successfully obtained two derivatives(TECA)PbBr_(3) and(TEBA)PbBr_(3)(TECA=triethylchloromethylammonium and TEBA=triethylbromomethylammonium).Halogen engineering successfully introduces halogen-halogen interactions between PbBr_(3) n-inorganic frameworks and organic cations,which increases the stretching distortion of the PbBr_(6) octahedral framework of(TECA)PbBr_(3) and(TEBA)PbBr_(3),accompanied by prominent orange-red broadband emission behavior in(TECA)PbBr_(3) and(TEBA)PbBr_(3).Meanwhile,the phase transition temperatures(Tp)of(TECA)PbBr_(3) and(TEBA)PbBr_(3) have also been significantly increased compared to(TEMA)PbBr_(3),and two derivatives demonstrated switchable dielectric responses.Impressively,the reversible structural phase transition of(TECA)PbBr_(3) and(TEBA)PbBr_(3) dominates the outright PL quenching behavior,while still maintaining high PL emission intensity below the Tp.This represents a rare and extraordinary phenomenon in the realm of bistable responsive materials.This work provides a feasible strategy for designing and modulating photoluminescent phase transition materials and deepens understanding of the structural-performance relationship.
基金supported by the National Natural Science Foundation of China(grant number 22201134)the Natural Science Foundation for Colleges and Universities of Jiangsu Province(grant number 22KJB150028)The authors would like to thank Yanbo Times(https://www.yanbotimes.cn)for support with TG analysis.
文摘Three-dimensional anion frameworks loaded with small cationic molecules are often reasonable models for the design of switching materials.However,due to limitations of the bond length and structural stability,it is difficult for the framework to carry larger molecules,so it is still a challenge to construct frameworks with larger capacities.
基金supported by the National Natural Science Foundation of China(21875251,21622108,21833010,21525104)the NSF of Fujian Province(2018H0047)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB20010200).
文摘Organic-inorganic hybrids have shown great potential for assembling dielectric phase transition materials,due to their unique characteristics and structural diversities.Here,we construct a new organic-organic hybrid,(cyclopropylaminium)_(3)BiBr_(6)(1),which consists of a zero-dimensional inorganic framework of BiBr_(6)octahedra and ternary cyclic organic cations.
基金D.H.L.acknowledges support from the National Natural Science Foundation of China(No.61674060)Innovation Fund of WNLO and the Fundamental Research Funds for the Central Universities,HUST(Nos.2017KFYXJJ030,2017KFXKJC003,2017KFXKJC002,and 2018KFYXKJC016)H.M.L.is grateful for support from New Mexico EPSCoR with NSF-1301346.We thank Testing Center of Huazhong University of Science and Technology for the support in inductively coupled plasma etching.
文摘Surface depletion field would introduce the depletion region near surface and thus could significantly alter the optical,electronic and optoelectronic properties of the materials,especially low-dimensional materials.Two-dimensional(2D)organic—inorganic hybrid perovskites with van der Waals bonds in the out-of-plane direction are expected to have less influence from the surface depletion field;nevertheless,studies on this remain elusive.Here we report on how the surface depletion field affects the structural phase transition,quantum confinement and Stark effect in 2D(BA)2PbI4 perovskite microplates by the thickness-,temperature-and power-dependent photoluminescence(PL)spectroscopy.Power dependent PL studies suggest that high-temperature phase(HTP)and low-temperature phase(LTP)can coexist in a wider temperature range depending on the thickness of the 2D perovskite microplates.With the decrease of the microplate thickness,the structural phase transition temperature first gradually decreases and then increases below 25 nm,in striking contrast to the conventional size dependent structural phase transition.Based on the thickness evolution of the emission peaks for both high-temperature phase and low-temperature phase,the anomalous size dependent phase transition could probably be ascribed to the surface depletion field and the surface energy difference between polymorphs.This explanation was further supported by the temperature dependent PL studies of the suspended microplates and encapsulated microplates with graphene and boron nitride flakes.Along with the thickness dependent phase transition,the emission energies of free excitons for both HTP and LTP with thickness can be ascribed to the surface depletion induced confinement and Stark effect.
基金supported by the Stable Support Plan Program of Shenzhen Natural Science Fund(no.20200925151834005)the National Natural Science Foundation of China(nos.21671095,21901108,and 22173043)。
文摘The engineering of switchable materials with controllable stimuli-responsive multistability remains challenging in materials science.Herein,we present syntheses and structural and magnetic studies of a one-dimensional cobalt(Ⅱ)coordination polymer[(enbzp)Co(bpy)](ClO_(4))_(2)·-MeOH·H2O(1;enbzp=N,N′-(ethane-1,2-diyl)bis(1-phenyl-1-(pyridin-2-yl)methanimine,bpy=4,4′-bipyridine)and its desolvated analogue[(enbzp)Co(bpy)](ClO_(4))_(2)(2),obtained by reversible single-crystal-to-single-crystal(SCSC)transformation.
基金supported by the National Key Research and Development Program of China(Grant No.2017YFA0302904)the National Natural Science Foundation of China(Grant Nos.11674377,and 11634015)+2 种基金the Chinese Academy of Sciences(Grant No.XDB07020200)supported by research grants from Japan Society for the Promotion of Science(JSPS)(Grant No.16H0401618)supported by the Youth Innovation Promotion Association of Chinese Academy of Sciences
文摘We report^(75) As nuclear magnetic resonance(NMR)/nuclear quadrupole resonance(NQR) and transmission electron microscopy(TEM) studies on LaFeAsO_(1-x)F_x. There are two superconducting domes in this material. The first one appears at 0.03 ≤ x ≤0.2 with T_c^(max) = 27 K, and the second one at 0.25 ≤x≤0.75 with T_c^(max) = 30 K. By NMR and TEM, we demonstrate that a C4-to-C2 structural phase transition(SPT) takes place above both domes, with the transition temperature T_s varying strongly with x. In the first dome, the SPT is followed by an antiferromagnetic(AF) transition, but neither AF order nor low-energy spin fluctuations are found in the second dome. By ^(75) As nuclear spin-lattice relaxation rate(1/T_1) measurements, we find that AF order and superconductivity coexist microscopically in LaFeAsO_(0.97) F_(0.03). In the coexisting region, 1/T_1 decreases at T_c but becomes proportional to T below 0.6 T_c, indicating gapless excitations. Therefore, in contrast to the early reports, the obtained phase diagram for x ≤ 0.2 is quite similar to the doped BaFe_2As_2 system. The electrical resistivity p in the second dome can be fitted by ρ = ρ0 + AT^n with n = 1 and a maximal coefficient A at around xopt = 0.5-0.55 at which T_s extrapolates to zero and Tc is the maximal, which suggests the importance of quantum critical fluctuations associated with the SPT. We have constructed a complete phase diagram of LaFeAsO_(1-x)F_x, which provides insight into the relationship between SPT, antiferromagnetism and superconductivity.
基金supported by the National Natural Science Foundation of China(22071273 and 21821003)Fundamental Research Funds for the Central Universities,Sun Yat Sen University(23lgzy001).
文摘In the realm of molecular phase transition research,particularly for applications in sensors,data storage and switching technologies,the role of organic-inorganic hybrid perovskite materials has been increasingly recognized for their significant potential.Nevertheless,hybrid post-perovskites,as a critical subclass of perovskites,have not been thoroughly studied and mainly limit in the instances based on polyatomic bridging agents like dicyanamide(dca^(-))and non-cyclic organic cations.Herein,a polar cyclic quaternary ammonium cation,N,N-dimethylpyrrolidinium(DMP^(+)),was used to assemble a new hybrid post-perovskite,(DMP)[Mn(dca)_(3)](1),which undergoes a phase transition from orthorhombic Bmmb to monoclinic P2_(1)/n space group at 249 K.By employing multiple techniques such as differential scanning calorimetry,variable-temperature single-crystal X-ray analysis,dielectric measurements,and Hirshfeld surface analysis,we disclosed the role of polar cyclic quaternary ammonium DMP^(+)in elevating the phase-transition temperature by 48 K,generating significant dielectric switching effect and facilitating interlayer sliding of inorganic framework.
文摘The structural, electronic and mechanical properties of transition metal hydrides （TMH, TM=Mo, Tc, Ru） are investigated by means of first principles calculation based on density fimctional theory with generalized gradient approximation. Among the five crystallographic structures that have been investigated, the cubic phase is found to be more stable than the hexagonal ones. A structural phase transition from ZB to WC in Moll, NaC1 to NiAs in TcH and NaCI to ZB to NiAs in RuH is also predicted under high pressure. The calculated elastic constants indicate that all the three hydrides are mechanically stable at ambient pressure.
基金Project supported by the National Key Research and Development Program of China(Grant Nos.2021YFA1601100 and 2017YFA0303104)the SPC-Lab Research Fund(Grant No.WDZC201901)+3 种基金the Science Challenge Project(Grant Nos.TZ2016004 and TZ2018002)the National Natural Science Foundation of China(Grant Nos.U1630248,11774320,and 11904334)Special Funds of Institute of Materials(Grant No.TP02201904)the Development Funds(Grant No.JZX7Y201901SY00900107)。
文摘The hybridization between the localized 4f level(f) with conduction(c) electrons in γ-Ce upon cooling has been previously revealed in single crystalline thin films experimentally and theoretically, whereas its influence on the γ → α phase transition was not explicitly verified, due to the fact that the phase transition happened in the bulk-layer, leaving the surface in the γ phase. Here in our work, we circumvent this issue by investigating the effect of alloying addition of La on Ce, by means of crystal structure, electronic transport and angle resolved photoemission spectroscopy measurements, together with a phenomenological periodic Anderson model and a modified Anderson impurity model. Our current researches indicate that the weakening of f–c hybridization is the major factor in the suppression of γ → α phase transition by La doping. The consistency of our results with the effects of other rare earth and actinide alloying additions on the γ → α phase transition of Ce is also discussed. Our work demonstrates the importance of the interaction between f and c electrons in understanding the unconventional phase transition in Ce, which is intuitive for further researches on other rare earth and actinide metals and alloys with similar phase transition behaviors.
基金supported by National Natural Science Foundation of China (No. 21561030)Prophase-sustentation Fund of Xinjiang Agricultural University (Nos. XJAU201410 and XJAU201511)
文摘A novel inorganic-organic hybrid supramolecular compound,[（3-nitroanilinium^＋）（18-crown-6）][IO4]（CH3OH）（1）,was discovered as phase-transition materials displaying dielectric anomalous behaviors.The yellow block crystal formed by N-H…O hydrogen bonding that made contact through the cavity of 18-crown-6 was characterized by single-crystal X-ray diffraction,elemental analysis,infrared analysis,thermogravimetric analysis,differential scanning calorimetry,and potential-energy calculations.Differential scanning calorimetry measurements indicate that the compound experiences a reversible phase transition at around 220 K.Temperature-dependent dielectric measurements further confirm the phase transitions.Potential-energy calculations demonstrate that the phase transition occurs due to the molecular order-disorder rotation of CH3OH,whereas the space grouping of the crystal remains unchanged.
基金supported by the National Natural Science Foundation of China (No. 21101025)
文摘A new phase transition compound,2-methoxyanilinium perchlorate-18-crown-6（1） {（oCH3OC6H4NH3）＋（18-crown-6） ClO4 },has been synthesized and separated as crystals.Differential scanning calorimetry（DSC） measurements show a pair of sharp peaks at 225 K（heating） and 210 K（cooling）,indicating the phase transition is first-order.Dielectric anomalies observed at 225 K（heating）and 210 K（cooling） further confirm the phase transition.The crystal structures determined at 298 K and123 K are both triclinic in P 1.The most distinct difference between room-temperature and lowtemperature structures is the order–disorder transition of the host 18-crown-6 molecule,which is the driving force of the phase transition.
基金Funded by the National Natural Science Foundation of China(No.11547115)the Science Research Foundation for Ph D of Liaoning Province(No.201501091)
文摘The atomic geometry, structure stability, electronic and magnetic properties of VSe2 were systematically investigated based on the density functional theory（DFT）. Varying from 3D to 2D four VSe2 structures, bulk 2H-VSe2 and 1T-VSe2, monolayer H-VSe2 and T-VSe2 are all demonstrated as thermodynamically stable by lattice dynamic calculations. More interestingly, the phase transition temperature is dramatically different due to the lattice size. Finally, owing to different crystal structures, H-VSe2 is semimetallic whereas T-VSe2 is totally metallic and also they have different magnetic moments. Our main argument is that being exfoliated from bulk to monolayer, 2H-VSe2 transforms to T-VSe2, accompanied by both semimetallic-metallic transition and dramatic magnetic moment variation. Our calculations provide a novel structure phase transition and an efficient way to modulate the electronic structure and magnetic moment of layered VSe2, which suggests potential applications as high-performance functional nanomaterial.
