Spin-orbit coupling(SOC)plays a vital role in determining the ground state and forming novel electronic states of matter where heavy elements are involved.Here,the prototypical perovskite iridate oxide SrIrO_(3)is inv...Spin-orbit coupling(SOC)plays a vital role in determining the ground state and forming novel electronic states of matter where heavy elements are involved.Here,the prototypical perovskite iridate oxide SrIrO_(3)is investigated to gain more insights into the SOC effect in the modification of electronic structure and corresponding magnetic and electrical properties.The high pressure metastable orthorhombic SrIrO_(3)is successfully stabilized by physical and chemical pressures,in which the chemical pressure is induced by Ru doping in Ir site and Mg substitution of Sr position.Detailed structural,magnetic,electrical characterizations and density functional theory(DFT)calculations reveal that the substitution of Ru for Ir renders an enhanced metallic characteristic,while the introduction of Mg into Sr site results in an insulating state with 10.1%negative magnetoresistance at 10 K under 7 T.Theoretical calculations indicate that Ru doping can weaken the SOC effect,leading to the decrease of orbital energy difference between J_(1/2)and J_(3/2),which is favorable for electron transport.On the contrary,Mg doping can enhance the SOC effect,inducing a metal-insulator-transition(MIT).The electronic phase transition is further revealed by DFT calculations,confirming that the strong SOC and electron-electron interactions can lead to the emergence of insulating state.These findings underline the intricate correlations between lattice degrees of freedom and SOC in determining the ground state,which effectively stimulate the physical pressure between like structures by chemical compression.展开更多
High-pressure and high-temperature(HPHT)experiments in large-volume presses(LVPs)benefit from reliable,available,and affordable heaters to achieve stable and homogeneous heating and,in some circumstances,X-ray transpa...High-pressure and high-temperature(HPHT)experiments in large-volume presses(LVPs)benefit from reliable,available,and affordable heaters to achieve stable and homogeneous heating and,in some circumstances,X-ray transparency for monitoring of properties of an in situ experiment using X-ray diffraction and contrast imaging techniques.We have developed heaters meeting the above requirements,and we screen the ternary system TiB2–SiC–hexagonal(h)BN(denoted as TSB)to enable manufacture of X-ray transparent heaters for HPHT runs.Heaters fabricated using optimized TSB-631(60%TiB2–30%SiC–10%hBN by weight)have been tested in modified truncated assemblies,showing excellent performance up to 22 GPa and 2395 K in HPHT runs.TSB-631 has good ceramic machinability,outstanding reproducibility,high stability,and negligible temperature gradient for runs at 3–7 GPa with cell assemblies with truncated edge lengths of 8–12 mm.The fabricated heaters not only show excellent performance in HPHT runs,but also demonstrate high X-ray transparency over a wide X-ray wavelength region,indicating potential applications for in situ X-ray diffraction/imaging under HPHT conditions in LVPs and other high-pressure apparatus.展开更多
The exploratory synthesis and structural characterization of twodimensional(2D)honeycomb structured Ru-based compounds are key focuses in inorganic materials research,due to the various exotic electronic states arisin...The exploratory synthesis and structural characterization of twodimensional(2D)honeycomb structured Ru-based compounds are key focuses in inorganic materials research,due to the various exotic electronic states arising from the interplay of electron correlations and spinorbit coupling.Among these compounds,α-RuCl_(3) and RuBr_(3) are considered as the most promising candidates for quantum spin liquid(QSL)materials[1–3].As a homolog,α-RuI3 has attracted significant interest,but it still remains relatively unexplored.Recently,it was synthesized by high-temperature and high-pressure solid-state reaction,but reported to be different crystal structures by independent groups.Ni et al.and Nawa et al.considerα-RuI3 to be R-3(3R)and P-31c(2H)space group,respectively[4,5].Both structures have typical 2D characteristics,in which the edge-sharing RuI6 octahedra form honeycomb layers stacked along the c-axis.The primary difference lies in that the honeycomb layers stack in ABCABC mode in the 3R phase,while in ABAB mode in the 2H phase(Fig.S1).Yang et al.discussed the stability of 3R and 2H polymorphs in terms of the total energies and dynamics,finding both structures are stable.However,the total energy of the 2H phase is slightly higher,2.58 meV than that of the 3R analog[6].When it comes to the conductivity behaviour,α-RuCl3 andα-RuBr_(3) are semiconductors as normally observed in QSL materials.In contrast,α-RuI_(3) exhibits metallic response.In 2D materials,the band structure may be drastically modified by altering the stacking order[7].Hence,determining the crystal structure ofα-RuI_(3) is urgently required,which is a key step in comprehensive and in-depth analysis of its physical properties.展开更多
Compared to AgNbO_(3) based ceramics, the experimental investigations on the single crystalline AgNbO_(3), especially the ground state and ferroic domain structures, are not on the same level. Here, based on successfu...Compared to AgNbO_(3) based ceramics, the experimental investigations on the single crystalline AgNbO_(3), especially the ground state and ferroic domain structures, are not on the same level. Here, based on successfully synthesized AgNbO_(3) single crystal using a flux method, we observed the coexistence of ferroelastic and ferroelectric domain structures by a combination study of polarized light microscopy and piezoresponse force microscopy.This finding may provide a new aspect for studying AgNbO_(3). The result also suggests a weak electromechanical response from the ferroelectric phase of AgNbO_(3), which is also supported by the transmission electron microscope characterization. Our results reveal that the AgNbO_(3) single crystal is in a polar ferroelectric phase at room temperature, clarifying its ground state which is controversial from the AgNbO_(3) ceramic materials.展开更多
The similarity of local structure-connection pattern and volumetrically compressive strain between host and vip phases can be used to stabilize heteroid metastable matter and tune the local structure and properties....The similarity of local structure-connection pattern and volumetrically compressive strain between host and vip phases can be used to stabilize heteroid metastable matter and tune the local structure and properties.Here a series of metastable ABO_(3)(A=Mn;B=Mn_(0.5)Mo_(0.5),Mn_(1/3)Ta_(2/3),and Mn_(0.5)Ta_(0.5)) were trapped in LiTaO_(3) to form solid-solutions,where the difference of solid solubility limit reveals the barrier of size effect on chemical pressure.All samples show antiferromagnetic characters,in which the(LiTaO_(3))_(1-x)-[Mn(Mn_(0.5)Mo_(0.5))O_(3)]_(x) series exhibit more complex magnetic and dielectric behaviors with the increasing of metastable vip phase,stemming from the complex interactive mechanism between Mn^(2+)and Mo^(6+).The cell parameter variation of (LiTaO_(3))_(1-z)-[Mn(Mn_(0.5)Ta_(0.5))O_(3)]_zshows a more regularly changing tendency,on account of the smallest size barrier.These findings show that chemical pressure can effectively stimulate the physical pressure to intercept and modulate a metastable phase at atomic-scale by compressibility effect between like structures at ambient pressure.展开更多
The intricate correlation between multiple degrees of freedom and physical properties is a fascinating area in solid state chemistry and condensed matter physics.Here,we report a quantum-magnetic system BaNi_(2)V_(2)O...The intricate correlation between multiple degrees of freedom and physical properties is a fascinating area in solid state chemistry and condensed matter physics.Here,we report a quantum-magnetic system BaNi_(2)V_(2)O_(8)(BNVO),in which the spin correlation was modulated by unusual oxidation state,leading to different magnetic behavior.The BNVO was modified with topochemical reduction(TR)to yield TR-BNVO with partially reduced valance state of Ni^(+)in the two-dimensional NiO_(6)-honeycomb lattice.Accordingly,the antiferromagnetic order is suppressed by the introduction of locally interposed Ni^(+)and oxygen vacancies,resulting in a ferromagnetic ground state with the transition temperature up to 710 K.A positive magnetoresistance(7.5%)was observed in the TR-BNVO at 40 K under 7 T.These findings show that topological reduction is a powerful approach to engineer low-dimensional materials and accelerate the discovery of new quantum magnetism.展开更多
The intricate correlation between charge degrees of freedom and physical properties is a fascinating area of research in solid state chemistry and condensed matter physics.Herein,we report on the pressureinduced succe...The intricate correlation between charge degrees of freedom and physical properties is a fascinating area of research in solid state chemistry and condensed matter physics.Herein,we report on the pressureinduced successive charge transfer and accompanied resistive evolution in honeycomb layered ruthenate AgRuO_(3).Structural revisiting and spectroscopic analyses affirm the ilmenite type R-3 structure with mixed valence cations as Ag^(+1/+2)Ru^(+4/+5)O_(3) at ambient pressure.In-situ pressure-and temperature-dependent resistance variation reveals a successive insulatormetal-insulator transition upon pressing,accompanied by unprecedented charge transfer between Ag and Ru under applied pressure,and a further structural phase transition in the insulator region at higher pressure.These phenomena are also corroborated by in-situ pressure-dependent Raman spectra,synchrotron X-ray diffraction,bond valence sums,and electronic structure calculations,emphasizing the dominated rare Ag2+,and near zero thermal expansion in the ab-plane in the metallic zone mostly due to the Jahn-Teller effect of d9-Ag2+.The multiple electronic instabilities in AgRuO_(3) may offer new possibilities toward novel and unconventionally physical and chemical behaviors in strongly correlated honeycomb lattices.展开更多
The chemical synthesis of functional materials is inseparable from national defense,medical treatment,national economy,and people’s livelihood.Traditional organic and inorganic materials are approaching their perform...The chemical synthesis of functional materials is inseparable from national defense,medical treatment,national economy,and people’s livelihood.Traditional organic and inorganic materials are approaching their performance limit.Therefore,the design and exploitation of novel functional materials are imminent and of significance for sustainable development.This review outlines the current progress and future prospects of chemical synthesis driven by high pressure,including organic and inorganic synthesis,as well as high-pressure phase retention.Based on the latest works,the basic mechanism of high-pressure chemical synthesis and three potential strategies for high-pressure phase harvesting are revealed.Finally,the challenge and outlook of high-pressureguided chemical synthesis are summarized.We sincerely hope that this review will provide guidance for designing high-performance materials by expanding the paths of chemical synthesis,thus greatly exploiting the existing materials world with newly emerging and enhanced functionalities.展开更多
基金supported by the National Natural Science Foundation of China(NSFC,No.22090041)the Guangdong Basic and Applied Basic Research Foundation(No.2022B1515120014)。
文摘Spin-orbit coupling(SOC)plays a vital role in determining the ground state and forming novel electronic states of matter where heavy elements are involved.Here,the prototypical perovskite iridate oxide SrIrO_(3)is investigated to gain more insights into the SOC effect in the modification of electronic structure and corresponding magnetic and electrical properties.The high pressure metastable orthorhombic SrIrO_(3)is successfully stabilized by physical and chemical pressures,in which the chemical pressure is induced by Ru doping in Ir site and Mg substitution of Sr position.Detailed structural,magnetic,electrical characterizations and density functional theory(DFT)calculations reveal that the substitution of Ru for Ir renders an enhanced metallic characteristic,while the introduction of Mg into Sr site results in an insulating state with 10.1%negative magnetoresistance at 10 K under 7 T.Theoretical calculations indicate that Ru doping can weaken the SOC effect,leading to the decrease of orbital energy difference between J_(1/2)and J_(3/2),which is favorable for electron transport.On the contrary,Mg doping can enhance the SOC effect,inducing a metal-insulator-transition(MIT).The electronic phase transition is further revealed by DFT calculations,confirming that the strong SOC and electron-electron interactions can lead to the emergence of insulating state.These findings underline the intricate correlations between lattice degrees of freedom and SOC in determining the ground state,which effectively stimulate the physical pressure between like structures by chemical compression.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.22090041 and 22401297)the Guangdong Basic and Applied Basic Research Foundation(Grant No.2022B1515120014).
文摘High-pressure and high-temperature(HPHT)experiments in large-volume presses(LVPs)benefit from reliable,available,and affordable heaters to achieve stable and homogeneous heating and,in some circumstances,X-ray transparency for monitoring of properties of an in situ experiment using X-ray diffraction and contrast imaging techniques.We have developed heaters meeting the above requirements,and we screen the ternary system TiB2–SiC–hexagonal(h)BN(denoted as TSB)to enable manufacture of X-ray transparent heaters for HPHT runs.Heaters fabricated using optimized TSB-631(60%TiB2–30%SiC–10%hBN by weight)have been tested in modified truncated assemblies,showing excellent performance up to 22 GPa and 2395 K in HPHT runs.TSB-631 has good ceramic machinability,outstanding reproducibility,high stability,and negligible temperature gradient for runs at 3–7 GPa with cell assemblies with truncated edge lengths of 8–12 mm.The fabricated heaters not only show excellent performance in HPHT runs,but also demonstrate high X-ray transparency over a wide X-ray wavelength region,indicating potential applications for in situ X-ray diffraction/imaging under HPHT conditions in LVPs and other high-pressure apparatus.
基金supported by the National Natural Science Foundation of China(No.22090041)the Program for Guangdong Introducing Innovative and Entrepreneurial Teams(No.2017ZT07C069)+1 种基金the Guangdong Basic and Applied Basic Research Foundation(No.2022B1515120014)the Natural Science Foundation of Zhejiang Province(No.LQ21A040010).
文摘The exploratory synthesis and structural characterization of twodimensional(2D)honeycomb structured Ru-based compounds are key focuses in inorganic materials research,due to the various exotic electronic states arising from the interplay of electron correlations and spinorbit coupling.Among these compounds,α-RuCl_(3) and RuBr_(3) are considered as the most promising candidates for quantum spin liquid(QSL)materials[1–3].As a homolog,α-RuI3 has attracted significant interest,but it still remains relatively unexplored.Recently,it was synthesized by high-temperature and high-pressure solid-state reaction,but reported to be different crystal structures by independent groups.Ni et al.and Nawa et al.considerα-RuI3 to be R-3(3R)and P-31c(2H)space group,respectively[4,5].Both structures have typical 2D characteristics,in which the edge-sharing RuI6 octahedra form honeycomb layers stacked along the c-axis.The primary difference lies in that the honeycomb layers stack in ABCABC mode in the 3R phase,while in ABAB mode in the 2H phase(Fig.S1).Yang et al.discussed the stability of 3R and 2H polymorphs in terms of the total energies and dynamics,finding both structures are stable.However,the total energy of the 2H phase is slightly higher,2.58 meV than that of the 3R analog[6].When it comes to the conductivity behaviour,α-RuCl3 andα-RuBr_(3) are semiconductors as normally observed in QSL materials.In contrast,α-RuI_(3) exhibits metallic response.In 2D materials,the band structure may be drastically modified by altering the stacking order[7].Hence,determining the crystal structure ofα-RuI_(3) is urgently required,which is a key step in comprehensive and in-depth analysis of its physical properties.
基金Supported by the National Natural Science Foundation of China(Grant Nos.11572040,11604011 and 51972028)the National Key Research and Development Program of China(Grant No.2019YFA0307900)+1 种基金Beijing Natural Science Foundation(Grant No.Z190011)the Technological Innovation Project of Beijing Institute of technology。
文摘Compared to AgNbO_(3) based ceramics, the experimental investigations on the single crystalline AgNbO_(3), especially the ground state and ferroic domain structures, are not on the same level. Here, based on successfully synthesized AgNbO_(3) single crystal using a flux method, we observed the coexistence of ferroelastic and ferroelectric domain structures by a combination study of polarized light microscopy and piezoresponse force microscopy.This finding may provide a new aspect for studying AgNbO_(3). The result also suggests a weak electromechanical response from the ferroelectric phase of AgNbO_(3), which is also supported by the transmission electron microscope characterization. Our results reveal that the AgNbO_(3) single crystal is in a polar ferroelectric phase at room temperature, clarifying its ground state which is controversial from the AgNbO_(3) ceramic materials.
基金financially supported by the National Natural Science Foundation of China(NSFC,Nos.21875287,22090041,22105228 and 11804404)the China Postdoctoral Science Foundation(No.2021M693603)。
文摘The similarity of local structure-connection pattern and volumetrically compressive strain between host and vip phases can be used to stabilize heteroid metastable matter and tune the local structure and properties.Here a series of metastable ABO_(3)(A=Mn;B=Mn_(0.5)Mo_(0.5),Mn_(1/3)Ta_(2/3),and Mn_(0.5)Ta_(0.5)) were trapped in LiTaO_(3) to form solid-solutions,where the difference of solid solubility limit reveals the barrier of size effect on chemical pressure.All samples show antiferromagnetic characters,in which the(LiTaO_(3))_(1-x)-[Mn(Mn_(0.5)Mo_(0.5))O_(3)]_(x) series exhibit more complex magnetic and dielectric behaviors with the increasing of metastable vip phase,stemming from the complex interactive mechanism between Mn^(2+)and Mo^(6+).The cell parameter variation of (LiTaO_(3))_(1-z)-[Mn(Mn_(0.5)Ta_(0.5))O_(3)]_zshows a more regularly changing tendency,on account of the smallest size barrier.These findings show that chemical pressure can effectively stimulate the physical pressure to intercept and modulate a metastable phase at atomic-scale by compressibility effect between like structures at ambient pressure.
基金financially supported by the National Natural Science Foundation of China(NSFC,Nos.21875287,22090041)the Guangdong Basic and Applied Basic Research Foundation(No.2022B1515120014)。
文摘The intricate correlation between multiple degrees of freedom and physical properties is a fascinating area in solid state chemistry and condensed matter physics.Here,we report a quantum-magnetic system BaNi_(2)V_(2)O_(8)(BNVO),in which the spin correlation was modulated by unusual oxidation state,leading to different magnetic behavior.The BNVO was modified with topochemical reduction(TR)to yield TR-BNVO with partially reduced valance state of Ni^(+)in the two-dimensional NiO_(6)-honeycomb lattice.Accordingly,the antiferromagnetic order is suppressed by the introduction of locally interposed Ni^(+)and oxygen vacancies,resulting in a ferromagnetic ground state with the transition temperature up to 710 K.A positive magnetoresistance(7.5%)was observed in the TR-BNVO at 40 K under 7 T.These findings show that topological reduction is a powerful approach to engineer low-dimensional materials and accelerate the discovery of new quantum magnetism.
基金supported by the National Science Foundation of China(grant nos.NSFC-22090041,21875287,U1932217,11974246,12004252,12025408,11921004,11974432,and 92165204)the Program for Guangdong Introducing Innovative and Entrepreneurial Teams(grant no.2017ZT07C069)NKRDPC-2017YFA0206203,NKRDPC-2018YFA0306001.
文摘The intricate correlation between charge degrees of freedom and physical properties is a fascinating area of research in solid state chemistry and condensed matter physics.Herein,we report on the pressureinduced successive charge transfer and accompanied resistive evolution in honeycomb layered ruthenate AgRuO_(3).Structural revisiting and spectroscopic analyses affirm the ilmenite type R-3 structure with mixed valence cations as Ag^(+1/+2)Ru^(+4/+5)O_(3) at ambient pressure.In-situ pressure-and temperature-dependent resistance variation reveals a successive insulatormetal-insulator transition upon pressing,accompanied by unprecedented charge transfer between Ag and Ru under applied pressure,and a further structural phase transition in the insulator region at higher pressure.These phenomena are also corroborated by in-situ pressure-dependent Raman spectra,synchrotron X-ray diffraction,bond valence sums,and electronic structure calculations,emphasizing the dominated rare Ag2+,and near zero thermal expansion in the ab-plane in the metallic zone mostly due to the Jahn-Teller effect of d9-Ag2+.The multiple electronic instabilities in AgRuO_(3) may offer new possibilities toward novel and unconventionally physical and chemical behaviors in strongly correlated honeycomb lattices.
基金supported by the National Key R&D Program of China(grant nos.2022YFA1402300,2023YFA1406200,and 2019YFA0708502)the National Science Foundation of China(grant nos.22131006,12174144,12474009,22022101,and 22090041).
文摘The chemical synthesis of functional materials is inseparable from national defense,medical treatment,national economy,and people’s livelihood.Traditional organic and inorganic materials are approaching their performance limit.Therefore,the design and exploitation of novel functional materials are imminent and of significance for sustainable development.This review outlines the current progress and future prospects of chemical synthesis driven by high pressure,including organic and inorganic synthesis,as well as high-pressure phase retention.Based on the latest works,the basic mechanism of high-pressure chemical synthesis and three potential strategies for high-pressure phase harvesting are revealed.Finally,the challenge and outlook of high-pressureguided chemical synthesis are summarized.We sincerely hope that this review will provide guidance for designing high-performance materials by expanding the paths of chemical synthesis,thus greatly exploiting the existing materials world with newly emerging and enhanced functionalities.
