Zero-dimensional(0D)hybrid metal halides are under intensive investigation owing to their unique physical properties,such as the broadband emission from highly localized excitons that is promising for white-emitting l...Zero-dimensional(0D)hybrid metal halides are under intensive investigation owing to their unique physical properties,such as the broadband emission from highly localized excitons that is promising for white-emitting lighting.However,fundamental understanding of emission variations and structure–property relationships is still limited.Here,by using pressure processing,we obtain robust exciton emission in 0D(C_(9)NH_(20))_(6)Pb_(3)Br_(12) at room temperature that can survive to 80 GPa,the recorded highest value among all the hybrid metal halides.In situ experimental characterization and first-principles calculations reveal that the pressure-induced emission is mainly caused by the largely suppressed phonon-assisted nonradiative pathway.Lattice compression leads to phonon hardening,which considerably weakens the exciton–phonon interaction and thus enhances the emission.The robust emission is attributed to the unique structure of separated spring-like[Pb_(3)Br_(12)]^(6−)trimers,which leads to the outstanding stability of the optically active inorganic units.Our findings not only reveal abnormally robust emission in a 0D metal halide,but also provide new insight into the design and optimization of local structures of trimers and oligomers in lowdimensional hybrid materials.展开更多
Two-dimensional(2D)Ruddlesden-Popper(RP)halide perovskites with diverse structures and properties have drawn increasing attention due to their promising optoelectronic applications.Recently,a new all-inorganic Cs_(2)P...Two-dimensional(2D)Ruddlesden-Popper(RP)halide perovskites with diverse structures and properties have drawn increasing attention due to their promising optoelectronic applications.Recently,a new all-inorganic Cs_(2)Pb(SCN)_(2)Br_(2) has been reported that opens up new potential for the development of 2D RP perovskites.However,recent reports of unusual dual emissions and two-edge absorption in Cs_(2)Pb(SCN)_(2)Br_(2) have generated intense debate about its origin and remains controversial.Here,by combining continuous pressure tuning with in situ diagnostics,we have unambiguously revealed the underlying mechanisms that the 2D Cs_(2)Pb(SCN)_(2)Br_(2) exhibits an intrinsic blue emission at 2.66 eV and an absorption edge close to the emission peak.While the gradually formed CsPbBr_(3) is responsible for the green emission at 2.33 eV with the absorption shoulder at 2.41 eV.Furthermore,by fitting the temperature-dependent intensity of the intrinsic blue emission,we have determined the corrected value of exciton binding energy for 2D Cs_(2)Pb(SCN)_(2)Br_(2) to be 90 meV.Intriguingly,an emission enhancement of 2.5 times is achieved in Cs_(2)Pb(SCN)_(2)Br_(2) under a mild pressure within 0.8 GPa,caused by the pressuresuppressed exciton-phonon interaction.This work not only elucidates the origin of the dual emissions and two-edge absorption in Cs_(2)Pb(SCN)_(2)Br_(2),but it also provides a potential means to regulate and optimize the optoelectronic properties of 2D perovskites.展开更多
Numerous exotic properties have been discovered in Dirac Semimetals(DSMs) and Weyl Semimetals(WSMs). In a given DSM/WSM, the Dirac/Weyl nodes usually coexist with other bulk states, making their respective contributio...Numerous exotic properties have been discovered in Dirac Semimetals(DSMs) and Weyl Semimetals(WSMs). In a given DSM/WSM, the Dirac/Weyl nodes usually coexist with other bulk states, making their respective contribution elusive. In this work, we distinguish the role of bulk states from the tilted Dirac nodes on the transport properties in DSMs. Specifically, we applied pressure to a type-II DSM material, PtTe2, and studied its pressure modified electronic and lattice structure systematically by using in situ transport measurements and X-ray diffraction(XRD). A pressure-induced transition at about 20 GPa is revealed in the transport properties, while the layered lattice structure is robust against pressure as illustrated in XRD measurement results.Density functional theory(DFT) calculations suggest that this is originated from the Lifshitz transition in the bulk states. Our findings provide evidence to identify the bulk states' influence on transport from the topologically-protected DSM states in the DSM material.展开更多
基金supported by the National Nature Science Foundation of China(NSFC)(Grant Nos.U1930401 and 51527801)support from the National Science Foundation(Grant No.DMR-1709116)+2 种基金supported by the National Science Foundation–Earth Sciences(Grant No.EAR-1634415)the Department of Energy–GeoSciences(Grant No.DE-FG02-94ER14466)partially by COMPRES under NSF Cooperative Agreement No.EAR-1606856.
文摘Zero-dimensional(0D)hybrid metal halides are under intensive investigation owing to their unique physical properties,such as the broadband emission from highly localized excitons that is promising for white-emitting lighting.However,fundamental understanding of emission variations and structure–property relationships is still limited.Here,by using pressure processing,we obtain robust exciton emission in 0D(C_(9)NH_(20))_(6)Pb_(3)Br_(12) at room temperature that can survive to 80 GPa,the recorded highest value among all the hybrid metal halides.In situ experimental characterization and first-principles calculations reveal that the pressure-induced emission is mainly caused by the largely suppressed phonon-assisted nonradiative pathway.Lattice compression leads to phonon hardening,which considerably weakens the exciton–phonon interaction and thus enhances the emission.The robust emission is attributed to the unique structure of separated spring-like[Pb_(3)Br_(12)]^(6−)trimers,which leads to the outstanding stability of the optically active inorganic units.Our findings not only reveal abnormally robust emission in a 0D metal halide,but also provide new insight into the design and optimization of local structures of trimers and oligomers in lowdimensional hybrid materials.
基金supported by the National Natural Science Foundation of China(NSFC)(grant nos.22275004,U1930401,and 52325309)the Shanghai Science and Technology Committee(grant no.22JC1410300)+2 种基金the Shanghai Key Laboratory of Novel Extreme Condition Materials(grant no.22dz2260800)supported by the NSFC(grant no.22275077).Q.H.is supported by the CAEP Research(grant no.CX20210048)the Tencent Xplorer Prize(grant no.XPLORER-2020-1013).
文摘Two-dimensional(2D)Ruddlesden-Popper(RP)halide perovskites with diverse structures and properties have drawn increasing attention due to their promising optoelectronic applications.Recently,a new all-inorganic Cs_(2)Pb(SCN)_(2)Br_(2) has been reported that opens up new potential for the development of 2D RP perovskites.However,recent reports of unusual dual emissions and two-edge absorption in Cs_(2)Pb(SCN)_(2)Br_(2) have generated intense debate about its origin and remains controversial.Here,by combining continuous pressure tuning with in situ diagnostics,we have unambiguously revealed the underlying mechanisms that the 2D Cs_(2)Pb(SCN)_(2)Br_(2) exhibits an intrinsic blue emission at 2.66 eV and an absorption edge close to the emission peak.While the gradually formed CsPbBr_(3) is responsible for the green emission at 2.33 eV with the absorption shoulder at 2.41 eV.Furthermore,by fitting the temperature-dependent intensity of the intrinsic blue emission,we have determined the corrected value of exciton binding energy for 2D Cs_(2)Pb(SCN)_(2)Br_(2) to be 90 meV.Intriguingly,an emission enhancement of 2.5 times is achieved in Cs_(2)Pb(SCN)_(2)Br_(2) under a mild pressure within 0.8 GPa,caused by the pressuresuppressed exciton-phonon interaction.This work not only elucidates the origin of the dual emissions and two-edge absorption in Cs_(2)Pb(SCN)_(2)Br_(2),but it also provides a potential means to regulate and optimize the optoelectronic properties of 2D perovskites.
基金supported by the National Key Research Program of China(Grant No.2016YFA0300702)the National Basic Research Program of China(Grant No.2014CB921104)+5 种基金the Shanghai Municipal Natural Science Foundation(Grant Nos.18JC1411400,18ZR1403200,and 17ZR1442400)the National Natural Science Foundation of China(Grant No.U1530402)the National Natural Science Foundation of China(Grant No.11674188)China Postdoctoral Science Foundation(Grant No.2017M610221)Shanghai Sailing Program(Grant No.17YF1429000)the National Postdoctoral Program for Innovative Talents(Grant No.BX201600036)
文摘Numerous exotic properties have been discovered in Dirac Semimetals(DSMs) and Weyl Semimetals(WSMs). In a given DSM/WSM, the Dirac/Weyl nodes usually coexist with other bulk states, making their respective contribution elusive. In this work, we distinguish the role of bulk states from the tilted Dirac nodes on the transport properties in DSMs. Specifically, we applied pressure to a type-II DSM material, PtTe2, and studied its pressure modified electronic and lattice structure systematically by using in situ transport measurements and X-ray diffraction(XRD). A pressure-induced transition at about 20 GPa is revealed in the transport properties, while the layered lattice structure is robust against pressure as illustrated in XRD measurement results.Density functional theory(DFT) calculations suggest that this is originated from the Lifshitz transition in the bulk states. Our findings provide evidence to identify the bulk states' influence on transport from the topologically-protected DSM states in the DSM material.