There is a pressing demand for the development of novel birefringent crystals tailored for compact optical components,especially for crystals exhibiting large birefringence across a range of temperatures.This has comm...There is a pressing demand for the development of novel birefringent crystals tailored for compact optical components,especially for crystals exhibiting large birefringence across a range of temperatures.This has commonly been achieved by introducing various deformable groups with high polarizability anisotropy.In this study,we combined both rigid and deformable groups to synthesise a new birefringent crystal,Al_(2)Te_(2)MoO_(10),which demonstrates an exceptional birefringence value of 0.29@550 nm at room temperature.Not only is this higher birefringence than that of commercial crystals,but Al_(2)Te_(2)MoO_(10)exhibits excellent birefringence stability over a wide temperature range,from 123 to 503 K.In addition,the first-principles theory calculations and structural analyses suggest that although the rigid AlO_(6)groups do not make much contribution to the prominent birefringence,they nonetheless played a role in maintaining the structural anisotropy at elevated temperatures.Based on these findings,this paper proposes a novel structural design strategy to complement conventional approaches for developing optimal birefringent crystals under various environmental conditions.展开更多
Compared with borates, carbonates, nitrates and phosphates, sulfates have been ignored as nonlinear optical(NLO) materials for a long time. Recently, researchers started to realize sulfates which have the potential as...Compared with borates, carbonates, nitrates and phosphates, sulfates have been ignored as nonlinear optical(NLO) materials for a long time. Recently, researchers started to realize sulfates which have the potential as NLO materials, and synthesized some sulfate NLO materials by the water solution method and solvothermal method. However, all these sulfate NLO materials have the same problem of low thermal stability. Here, we synthesized a new Cs4 Mg6(SO4)8, which crystallizes in the orthorhombic space group P212121 with a = 9.102, b = 9.955, c = 16.127 ?, V = 1461.3 ?3, Z = 2, F(000) = 1352, μ = 5.777 mm-1, R = 0.0213 and wR = 0.0480. The single crystal structure can be described as a three-dimensional framework constructed by MgO6 octahedra and SO4 tetrahedra. Relevant optical measurements indicate that Cs4 Mg6(SO4)8 is short-wave ultraviolet transparent and has a moderate second harmonic generation response. Theoretical calculations by the CASTEP package reveal that S–O groups are NLO-active anionic groups. Significantly, Cs4 Mg6(SO4)8 has high thermal stability up to 781 ℃ based on thermal analyses. We believe that our work will provide a new strategy for researchers to develop new sulfate short-wave ultraviolet NLO materials of high thermal stability.展开更多
基金supported by the National Natural Science Foundation of China(22122507,61975207,22193042,21833010,and 21921001)the Natural Science Foundation of Fujian Province(2022J02012)+2 种基金the Youth Innovation Promotion Association of the Chinese Academy of Sciences(Y202069)the Key Research Program of Frontier Sciences of the Chinese Academy of Sciences(ZDBS-LYSLH024)the China Postdoctoral Science Foundation(2023M743498)。
文摘There is a pressing demand for the development of novel birefringent crystals tailored for compact optical components,especially for crystals exhibiting large birefringence across a range of temperatures.This has commonly been achieved by introducing various deformable groups with high polarizability anisotropy.In this study,we combined both rigid and deformable groups to synthesise a new birefringent crystal,Al_(2)Te_(2)MoO_(10),which demonstrates an exceptional birefringence value of 0.29@550 nm at room temperature.Not only is this higher birefringence than that of commercial crystals,but Al_(2)Te_(2)MoO_(10)exhibits excellent birefringence stability over a wide temperature range,from 123 to 503 K.In addition,the first-principles theory calculations and structural analyses suggest that although the rigid AlO_(6)groups do not make much contribution to the prominent birefringence,they nonetheless played a role in maintaining the structural anisotropy at elevated temperatures.Based on these findings,this paper proposes a novel structural design strategy to complement conventional approaches for developing optimal birefringent crystals under various environmental conditions.
基金This work was financially supported by the National Natural Science Foundation of China(22122507,21833010,61975207,22193042,and 21921001)the Natural Science Foundation of Fujian Province(2022J02012)+2 种基金the Youth Innovation Promotion Association of the Chinese Academy of Sciences(Y202069)the Key Research Program of Frontier Sciences of the Chinese Academy of Sciences(ZDBS-LY-SLH024)as well as Fujian Institute of Innovation(FJCXY18010201)in the Chinese Academy of Sciences.
基金financially supported by the National Natural Science Foundation of China(21833010,21571178,21601188,51872297,51802321)。
文摘Compared with borates, carbonates, nitrates and phosphates, sulfates have been ignored as nonlinear optical(NLO) materials for a long time. Recently, researchers started to realize sulfates which have the potential as NLO materials, and synthesized some sulfate NLO materials by the water solution method and solvothermal method. However, all these sulfate NLO materials have the same problem of low thermal stability. Here, we synthesized a new Cs4 Mg6(SO4)8, which crystallizes in the orthorhombic space group P212121 with a = 9.102, b = 9.955, c = 16.127 ?, V = 1461.3 ?3, Z = 2, F(000) = 1352, μ = 5.777 mm-1, R = 0.0213 and wR = 0.0480. The single crystal structure can be described as a three-dimensional framework constructed by MgO6 octahedra and SO4 tetrahedra. Relevant optical measurements indicate that Cs4 Mg6(SO4)8 is short-wave ultraviolet transparent and has a moderate second harmonic generation response. Theoretical calculations by the CASTEP package reveal that S–O groups are NLO-active anionic groups. Significantly, Cs4 Mg6(SO4)8 has high thermal stability up to 781 ℃ based on thermal analyses. We believe that our work will provide a new strategy for researchers to develop new sulfate short-wave ultraviolet NLO materials of high thermal stability.
