Birefringent crystals play a crucial role in regulating the polarization of light and are widely used in optoelectronic fields.However,the effective design of novel infrared(IR)birefringent crystals with large birefri...Birefringent crystals play a crucial role in regulating the polarization of light and are widely used in optoelectronic fields.However,the effective design of novel infrared(IR)birefringent crystals with large birefringence(Δn)still face significant challenges.In this study,we present the rational design and successful synthesis of two novel quinary oxychalcogenides with the formula Ba_(3)M^(II)Ge_(3)O_(2)S_(8)(M^(II)=Mn,Cd),employing a heteroanion-introduction strategy via high-temperature solid-state reactions.Ba_(3)M^(II)Ge_(3)O_(2)S_(8)(M^(II)=Mn,Cd)crystallized in the monoclinic space group P2_(1)/n(no.14)and the structures comprised one-dimensional(1D)[M^(II)Ge_(3)S_(8)O_(2)]^(6−)chains arranged in an antiparallel manner and separated by Ba^(2+)cations.The coexistence of multiple heteroanionic ligands([M^(II)OS_(5)]octahedra,[GeOS_(3)],and[GeO_(2)S_(2)]tetrahedra)in one material was surprisingly discovered for the first time in the realm of oxychalcogenides.It was revealed that the heteroanion-introduction strategy not only leads to a reduction in the structural dimensionality but also enhances the optical anisotropy significantly.Notably,Ba_(3)M^(II)Ge_(3)O_(2)S_(8)(M^(II)=Mn,Cd)demonstrated large Δn values of 0.11 and 0.14,which represent a remarkable improvement compared to the three-dimensional(3D)parent AE_(3)M^(II)M^(IV)_(2)Q_(8) system(Δn=0).Furthermore,theoretical calculations suggest that the significantΔn of Ba_(3)M^(II)Ge_(3)O_(2)S_(8)(M^(II)=Mn,Cd)resulted primarily from the combination of polarizabilities from the various heteroanionic groups.Overall,these results highlight the potential of the heteroanion-introduction strategy for designing novel IR birefringent materials for optoelectronic applications.展开更多
Much effort has been devoted to the discovery of novel birefringent crystals that display considerable birefringence(Δn)in the infrared(IR)region.However,the simultaneous achievement of a wide energy gap(E_(g)>3.1...Much effort has been devoted to the discovery of novel birefringent crystals that display considerable birefringence(Δn)in the infrared(IR)region.However,the simultaneous achievement of a wide energy gap(E_(g)>3.1 eV)and a largeΔn(>0.2)in a heteroanionic chalcogenide system remains a formidable challenge.To address this bottleneck,we applied the partial-substitution strategy and successfully designed and synthesized two new quaternary oxychalcogenides,namely AEGe_(2)O_(4)Se(AE=Sr and Ba).These two isomorphic compounds belong to the monoclinic space group P2_(1)/c(no.14),featuring a structure composed of two-dimensional(2D)[Ge_(2)O_(4)Se]^(2−)layers with an antiparallel arrangement,which are separated by charge-balanced Ba^(2+)cations.Remarkably,they exhibit the coexistence of largeΔn values(0.209 and 0.238@2050 nm based on the generalized gradient approximation)and wide E_(g)values(3.57 and 3.81 eV).Furthermore,theoretical calculations were performed to elucidate the interplay between optical properties and electronic structures.These results reveal that the significantly improvedΔn value(approximately 15–17 times that of the parent compound BaGe_(2)O_(5))can mainly be attributed to the newly discovered[GeO_(3)Se]heteroanionic motif.In brief,this study provides a simple chemical substitution method to overcome the trade-off between wide E_(g)and largeΔn values in heteroanionic chalcogenides.展开更多
A new family of oxychalcogenides,[Sr_(3)VO_(4)][MQ3](M=Ga,In,Q=S,Se),was successfully synthesized via the high-temperature flux method.The Ga analogues feature a centrosymmetric(P2_(1)/c)0-D structure containing isola...A new family of oxychalcogenides,[Sr_(3)VO_(4)][MQ3](M=Ga,In,Q=S,Se),was successfully synthesized via the high-temperature flux method.The Ga analogues feature a centrosymmetric(P2_(1)/c)0-D structure containing isolated[Ga(2)Q_(6)]6−dimers,[VO_(4)]^(5+)tetrahedra and Sr^(2+)ions,while the In analogues crystallize in a noncentrosymmetric(Pmc2_(1))1-D structure which comprises_(∞)[InQ_(3)]^(3−)chains,[VO_(4)]^(5+)tetrahedra and Sr^(2+)ions.The structural evolution from In to Ga analogues occurs once the Ga/In ratio increases higher than 62%/38%.[Sr_(3)VO_(4)][GaSe_(3)]and[Sr_(3)VO_(4)][InSe_(3)]possess optical band gaps of 2.51 and 2.62 eV,respectively.DFT calculations revealed their similar band edge compositions of the Se 4p-V 3d states.[Sr_(3)VO_(4)][InSe_(3)]exhibited a single PL emission band at 455 nm,while[Sr_(3)VO_(4)][GaSe_(3)]showed two emis-sion bands at 455 and 640 nm.The calculated SHG coefficients of[Sr_(3)VO_(4)][InS_(3)]and[Sr_(3)VO_(4)][InSe_(3)]are 10.8 and 6.9 times that of KDP.We suppose that this work would inspire the exploration of oxychalcogen-ide-based functional materials.展开更多
Atomically thin two-dimensional(2D)bismuth oxychalcogenides(Bi_(2)O_(2)X,X=S,Se,Te)have recently attracted extensive attention in the material research community due to their unique structure,outstanding long-term amb...Atomically thin two-dimensional(2D)bismuth oxychalcogenides(Bi_(2)O_(2)X,X=S,Se,Te)have recently attracted extensive attention in the material research community due to their unique structure,outstanding long-term ambient stability,and high carrier mobility,which enable them as promising candidates for high-performance electronic and optoelectronic applications.Herein,we present a comprehensive review on the recent advances of 2D bismuth oxychalcogenides research.We start with an introduction of their fundamental properties including crystal structure and electronic band structure.Next,we summarize the common techniques for synthesizing these 2D structures with high crystallinity and large lateral size.Furthermore,we elaborate on their device applications including transistors,artificial synapses,optical switch and photodetectors.The last but not the least,we summarize the existing challenges and prospects for this emerging 2D bismuth oxychalcogenides field.展开更多
A new layered Cu-based oxychalcogenide Ba_3Fe_2O_5Cu_2S_2 has been synthesized and its magnetic and electronic properties were revealed. Ba_3Fe_2O_5Cu_2S_2 is built up by alternatively stacking [Cu_2S_2]^（2-） layers...A new layered Cu-based oxychalcogenide Ba_3Fe_2O_5Cu_2S_2 has been synthesized and its magnetic and electronic properties were revealed. Ba_3Fe_2O_5Cu_2S_2 is built up by alternatively stacking [Cu_2S_2]^（2-） layers and iron perovskite oxide[（FeO_2）（BaO）（FeO_2）]^（2-）layers along the c axis that are separated by barium ions with Fe^（3＋） fivefold coordinated by a square-pyramidal arrangement of oxygen. From the bond valence arguments, we inferred that in layered CuC h-based（Ch =S, Se, Te） compounds the ＋3 cation in perovskite oxide sheet prefers a square pyramidal site, while the lower valence cation prefers the square planar sites. The studies on susceptibility, transport, and optical reflectivity indicate that Ba_3Fe_2O_5Cu_2S_2 is an antiferromagnetic semiconductor with a Ne′el temperature of 121 K and an optical bandgap of 1.03 eV. The measurement of heat capacity from 10 K to room temperature shows no anomaly at 121 K. The Debye temperature is determined to be 113 K. Theoretical calculations indicate that the conduction band minimum is predominantly contributed by O 2p and 3 d states of Fe ions that antiferromagnetically arranged in FeO_2 layers. The Fe 3d states are located at lower energy and result in a narrow bandgap in comparison with that of the isostructural Sr_3Sc_2O_5Cu_2S_2.展开更多
Layered oxychalcogenides namely the SmCrS_(2−x)Se_(x)O(x=0–2)solid solutions,were synthesized via high-temperature solid-state reactions.SmCrQ_(2)O(Q=S,Se)crystallizes in the monoclinic space group of C2/m(No.12),fea...Layered oxychalcogenides namely the SmCrS_(2−x)Se_(x)O(x=0–2)solid solutions,were synthesized via high-temperature solid-state reactions.SmCrQ_(2)O(Q=S,Se)crystallizes in the monoclinic space group of C2/m(No.12),featuring typical layered structures.The two-dimensional(2D)_(∞)^(2)[CrQ_(2)O]^(3−)motifs stack along the a axis,which are separated by Sm^(3+)ions.The_(∞)^(2)[CrQ_(2)O]^(3−)layers are composed of[CrQ_(6)]^(9−)and[CrQ_(4)O_(2)]^(9−)octahedra via corner and edge sharing.The in-plane Cr atoms feature a distorted honeycomb arrangement with prolonged Cr⋯Cr distances along the c axis.The powder X-ray diffraction results confirm the phase purities and the formation of solid solutions.Magnetic measurements indicate that the SmCrS_(2−x)Se_(x)O solid solutions show typical antiferromagnetic ordering.The Néer temperatures(TN)increase from 74 K to 121 K with the decrease in S content.展开更多
Birefringent crystals are crucial for manipulating light's phase and polarization,making them vital components in various optical devices.Traditionally,strategies for designing high-performance birefringent crysta...Birefringent crystals are crucial for manipulating light's phase and polarization,making them vital components in various optical devices.Traditionally,strategies for designing high-performance birefringent crystals have focused on modifying the parent structure.However,there are limited examples demonstrating how changing functional groups can effectively enhance birefringence(Δn),as such changes often significantly alter the crystal structure.In this study,we propose a“functional group implantation”strategy aiming at significantly improving birefringent performance within the chalcogenide system.This involves replacing the isotropic[S]^(2-)ions with anisotropicπ-conjugated[CO_(3)]^(2-)groups.We validated this approach through comprehensive comparisons between the chalcogenide[Ba_(3)S][GeS_(4)]and oxychalcogenide[Ba_(3)CO_(3)][MS_(4)](M=Ge and Sn),both of which adopt the same space group and feature the same arrangements of functional groups.Experimental characterization and theoretical calculations confirm that the[CO_(3)]^(2-)groups exhibit significantly greater polarization anisotropy than the[S]^(2-)groups.This difference leads to a marked increase inΔn in[Ba_(3)CO_(3)][MS_(4)](ranging from 0.088 to 0.112 at 546 nm)compared to[Ba_(3)S][GeS_(4)](0.021 at 546 nm).This finding not only broadens the structural chemistry ofπ-conjugated chalcogenides but also illustrates the potential of functional group implantation for designing infrared birefringent crystals with enhanced optical anisotropy.展开更多
基金supported by the National Natural Science Foundation of China(21771179)Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2021ZR118)the Natural Science Foundation of Fujian Province(2022L3092 and 2023H0041).
文摘Birefringent crystals play a crucial role in regulating the polarization of light and are widely used in optoelectronic fields.However,the effective design of novel infrared(IR)birefringent crystals with large birefringence(Δn)still face significant challenges.In this study,we present the rational design and successful synthesis of two novel quinary oxychalcogenides with the formula Ba_(3)M^(II)Ge_(3)O_(2)S_(8)(M^(II)=Mn,Cd),employing a heteroanion-introduction strategy via high-temperature solid-state reactions.Ba_(3)M^(II)Ge_(3)O_(2)S_(8)(M^(II)=Mn,Cd)crystallized in the monoclinic space group P2_(1)/n(no.14)and the structures comprised one-dimensional(1D)[M^(II)Ge_(3)S_(8)O_(2)]^(6−)chains arranged in an antiparallel manner and separated by Ba^(2+)cations.The coexistence of multiple heteroanionic ligands([M^(II)OS_(5)]octahedra,[GeOS_(3)],and[GeO_(2)S_(2)]tetrahedra)in one material was surprisingly discovered for the first time in the realm of oxychalcogenides.It was revealed that the heteroanion-introduction strategy not only leads to a reduction in the structural dimensionality but also enhances the optical anisotropy significantly.Notably,Ba_(3)M^(II)Ge_(3)O_(2)S_(8)(M^(II)=Mn,Cd)demonstrated large Δn values of 0.11 and 0.14,which represent a remarkable improvement compared to the three-dimensional(3D)parent AE_(3)M^(II)M^(IV)_(2)Q_(8) system(Δn=0).Furthermore,theoretical calculations suggest that the significantΔn of Ba_(3)M^(II)Ge_(3)O_(2)S_(8)(M^(II)=Mn,Cd)resulted primarily from the combination of polarizabilities from the various heteroanionic groups.Overall,these results highlight the potential of the heteroanion-introduction strategy for designing novel IR birefringent materials for optoelectronic applications.
基金National Natural Science Foundation of China(21771179)Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2021ZR118)Natural Science Foundation of Fujian Province(2022L3092 and 2023H0041)。
文摘Much effort has been devoted to the discovery of novel birefringent crystals that display considerable birefringence(Δn)in the infrared(IR)region.However,the simultaneous achievement of a wide energy gap(E_(g)>3.1 eV)and a largeΔn(>0.2)in a heteroanionic chalcogenide system remains a formidable challenge.To address this bottleneck,we applied the partial-substitution strategy and successfully designed and synthesized two new quaternary oxychalcogenides,namely AEGe_(2)O_(4)Se(AE=Sr and Ba).These two isomorphic compounds belong to the monoclinic space group P2_(1)/c(no.14),featuring a structure composed of two-dimensional(2D)[Ge_(2)O_(4)Se]^(2−)layers with an antiparallel arrangement,which are separated by charge-balanced Ba^(2+)cations.Remarkably,they exhibit the coexistence of largeΔn values(0.209 and 0.238@2050 nm based on the generalized gradient approximation)and wide E_(g)values(3.57 and 3.81 eV).Furthermore,theoretical calculations were performed to elucidate the interplay between optical properties and electronic structures.These results reveal that the significantly improvedΔn value(approximately 15–17 times that of the parent compound BaGe_(2)O_(5))can mainly be attributed to the newly discovered[GeO_(3)Se]heteroanionic motif.In brief,this study provides a simple chemical substitution method to overcome the trade-off between wide E_(g)and largeΔn values in heteroanionic chalcogenides.
基金supported by the National Natural Science Foundation of China(grant 22005006,22001263,21871008)the China Postdoctoral Science Foundation(grant 2019M660298 and 2020T130009)。
文摘A new family of oxychalcogenides,[Sr_(3)VO_(4)][MQ3](M=Ga,In,Q=S,Se),was successfully synthesized via the high-temperature flux method.The Ga analogues feature a centrosymmetric(P2_(1)/c)0-D structure containing isolated[Ga(2)Q_(6)]6−dimers,[VO_(4)]^(5+)tetrahedra and Sr^(2+)ions,while the In analogues crystallize in a noncentrosymmetric(Pmc2_(1))1-D structure which comprises_(∞)[InQ_(3)]^(3−)chains,[VO_(4)]^(5+)tetrahedra and Sr^(2+)ions.The structural evolution from In to Ga analogues occurs once the Ga/In ratio increases higher than 62%/38%.[Sr_(3)VO_(4)][GaSe_(3)]and[Sr_(3)VO_(4)][InSe_(3)]possess optical band gaps of 2.51 and 2.62 eV,respectively.DFT calculations revealed their similar band edge compositions of the Se 4p-V 3d states.[Sr_(3)VO_(4)][InSe_(3)]exhibited a single PL emission band at 455 nm,while[Sr_(3)VO_(4)][GaSe_(3)]showed two emis-sion bands at 455 and 640 nm.The calculated SHG coefficients of[Sr_(3)VO_(4)][InS_(3)]and[Sr_(3)VO_(4)][InSe_(3)]are 10.8 and 6.9 times that of KDP.We suppose that this work would inspire the exploration of oxychalcogen-ide-based functional materials.
基金Fundamental Research Funds for the Central Universities,Grant/Award Number:2019kfyXMBZ018Hubei Provincial Nature Science Foundation of China,Grant/Award Number:2019CFA002National Nature Science Foundation of China,Grant/Award Numbers:21825103,51727809。
文摘Atomically thin two-dimensional(2D)bismuth oxychalcogenides(Bi_(2)O_(2)X,X=S,Se,Te)have recently attracted extensive attention in the material research community due to their unique structure,outstanding long-term ambient stability,and high carrier mobility,which enable them as promising candidates for high-performance electronic and optoelectronic applications.Herein,we present a comprehensive review on the recent advances of 2D bismuth oxychalcogenides research.We start with an introduction of their fundamental properties including crystal structure and electronic band structure.Next,we summarize the common techniques for synthesizing these 2D structures with high crystallinity and large lateral size.Furthermore,we elaborate on their device applications including transistors,artificial synapses,optical switch and photodetectors.The last but not the least,we summarize the existing challenges and prospects for this emerging 2D bismuth oxychalcogenides field.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.51472266,51202286,and 91422303)the Strategic Priority Research Program(B)of the Chinese Academy of Sciences(Grant No.XDB07020100)the ICDD
文摘A new layered Cu-based oxychalcogenide Ba_3Fe_2O_5Cu_2S_2 has been synthesized and its magnetic and electronic properties were revealed. Ba_3Fe_2O_5Cu_2S_2 is built up by alternatively stacking [Cu_2S_2]^（2-） layers and iron perovskite oxide[（FeO_2）（BaO）（FeO_2）]^（2-）layers along the c axis that are separated by barium ions with Fe^（3＋） fivefold coordinated by a square-pyramidal arrangement of oxygen. From the bond valence arguments, we inferred that in layered CuC h-based（Ch =S, Se, Te） compounds the ＋3 cation in perovskite oxide sheet prefers a square pyramidal site, while the lower valence cation prefers the square planar sites. The studies on susceptibility, transport, and optical reflectivity indicate that Ba_3Fe_2O_5Cu_2S_2 is an antiferromagnetic semiconductor with a Ne′el temperature of 121 K and an optical bandgap of 1.03 eV. The measurement of heat capacity from 10 K to room temperature shows no anomaly at 121 K. The Debye temperature is determined to be 113 K. Theoretical calculations indicate that the conduction band minimum is predominantly contributed by O 2p and 3 d states of Fe ions that antiferromagnetically arranged in FeO_2 layers. The Fe 3d states are located at lower energy and result in a narrow bandgap in comparison with that of the isostructural Sr_3Sc_2O_5Cu_2S_2.
基金supported by the Innovation Program of the CAS(Grant KJCX2-EW-W11)the“Strategic Priority Research Program(B)”of the Chinese Academy of Sciences(Grants XDB04040200)+3 种基金the NSF of China(Grants 91122034,51125006,51202279,61376056,and 21201012)the Science and Technology Commission of Shanghai(Grant 12XD1406800)the Research Grant of Qian Xuesen Laboratory of Space Technology(Y-KC-WY-99-ZY-000-013)the Qian Xuesen Youth Innovation Fund(Y-KC-JT-QXS-012).
文摘Layered oxychalcogenides namely the SmCrS_(2−x)Se_(x)O(x=0–2)solid solutions,were synthesized via high-temperature solid-state reactions.SmCrQ_(2)O(Q=S,Se)crystallizes in the monoclinic space group of C2/m(No.12),featuring typical layered structures.The two-dimensional(2D)_(∞)^(2)[CrQ_(2)O]^(3−)motifs stack along the a axis,which are separated by Sm^(3+)ions.The_(∞)^(2)[CrQ_(2)O]^(3−)layers are composed of[CrQ_(6)]^(9−)and[CrQ_(4)O_(2)]^(9−)octahedra via corner and edge sharing.The in-plane Cr atoms feature a distorted honeycomb arrangement with prolonged Cr⋯Cr distances along the c axis.The powder X-ray diffraction results confirm the phase purities and the formation of solid solutions.Magnetic measurements indicate that the SmCrS_(2−x)Se_(x)O solid solutions show typical antiferromagnetic ordering.The Néer temperatures(TN)increase from 74 K to 121 K with the decrease in S content.
基金supported by the National Natural Science Foundation of China(22175175 and 22273081)Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2021ZR118)the Natural Science Foundation of Fujian Province(2022L3092 and 2023H0041).
文摘Birefringent crystals are crucial for manipulating light's phase and polarization,making them vital components in various optical devices.Traditionally,strategies for designing high-performance birefringent crystals have focused on modifying the parent structure.However,there are limited examples demonstrating how changing functional groups can effectively enhance birefringence(Δn),as such changes often significantly alter the crystal structure.In this study,we propose a“functional group implantation”strategy aiming at significantly improving birefringent performance within the chalcogenide system.This involves replacing the isotropic[S]^(2-)ions with anisotropicπ-conjugated[CO_(3)]^(2-)groups.We validated this approach through comprehensive comparisons between the chalcogenide[Ba_(3)S][GeS_(4)]and oxychalcogenide[Ba_(3)CO_(3)][MS_(4)](M=Ge and Sn),both of which adopt the same space group and feature the same arrangements of functional groups.Experimental characterization and theoretical calculations confirm that the[CO_(3)]^(2-)groups exhibit significantly greater polarization anisotropy than the[S]^(2-)groups.This difference leads to a marked increase inΔn in[Ba_(3)CO_(3)][MS_(4)](ranging from 0.088 to 0.112 at 546 nm)compared to[Ba_(3)S][GeS_(4)](0.021 at 546 nm).This finding not only broadens the structural chemistry ofπ-conjugated chalcogenides but also illustrates the potential of functional group implantation for designing infrared birefringent crystals with enhanced optical anisotropy.
