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
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.
