Non-covalent interactions play an indispensable role in the construction of molecular ferroelectrics,as they can regulate the relative orientation and stacking mode between molecules.However,the difficulty and challen...Non-covalent interactions play an indispensable role in the construction of molecular ferroelectrics,as they can regulate the relative orientation and stacking mode between molecules.However,the difficulty and challenge lie in precisely designing and regulating the weak intermolecular interactions,ultimately generating macroscopically reversible spontaneous polarization through synergistic effects,thereby achieving ferroelectricity.Herein,we introduced halogenated ammonium Cl-PA^(+)(Cl-PA^(+)is 3-chloropropylaminium)to regulate non-covalent interactions in the structure of hybrid perovskite,and constructed a photoferroelectric semiconductor(Cl-PA)_(2)PbCl_(4)with large piezoelectric coefficient(d_(33)=27.4 pC/N)and high Curie temperature(T_(c)=353 K)through the synergistic effect of hydrogen bonding and halogen-halogen interactions.Compared with non-ferroelectric(PA)_(2)PbCl_(4)(PA^(+)is n-propylaminium),the severe distortion of PbCl_(6)octahedra,weakened N-H…Cl hydrogen bond between organic cations and inorganic frameworks,enhanced C-H…Cl hydrogen bond between cations,and the additional Cl…Cl interaction in the structure synergistically induce the ferroelectricity of(Cl-PA)_(2)PbCl_(4).In addition,the large dipole moment of Cl-PA is also beneficial for constructing molecular ferroelectrics,and the syne rgetic effect of non-covale nt interactions in(Cl-PA)_(2)PbCl_(4)provides the possibility for dipole flipping and symmetry breaking.Therefore,constructing molecular ferroelectrics through the synergistic effect of non-covalent interactions essentially utilizes dynamic coupling and precise equilibrium of multiple weak interactions to achieve the formation,stability,and external field flipping of spontaneous polarization.Through this collaborative design,ferroelectrics with high spontaneous polarization(Ps),low coercive field,and wide temperature range can be achieved,which opens up new directions for flexible electronics and energy storage.展开更多
Polar two-dimensional organic-inorganic hybrid perovskites(2D-OIHPs)with the bulk photovoltaic effect(BPVE)have shown tremendous potential in developing passive high-performance polarized light detection(PLD)owing to ...Polar two-dimensional organic-inorganic hybrid perovskites(2D-OIHPs)with the bulk photovoltaic effect(BPVE)have shown tremendous potential in developing passive high-performance polarized light detection(PLD)owing to their polarization-driven strong light-matter interaction associated with excellent semiconductor properties.However,the current exploration of these materials for PLD is limited by trial-and-error approaches,which are time-consuming and resource-intensive,highlighting the need for the emergence of polar materials with robust design methods.In this study,we demonstrated the potential of a target-oriented synthesized chiral alternating cation-intercalated(ACI)OIHP,(R-PPA)(EA)PbBr4(1,R-PPA=(R)-(+)-1-phenylpropylamine,and EA=ethylamine),for high-sensitive passive PLD.Under steady illumination,1 exhibits obvious BPVE along the polar direction with a I_(on)/I_(off) ratio of≈103.Additionally,owing to the polarization-driven nature of BPVE,a single crystal device based on 1 exhibited significant angle-resolved short circuit current with a polarization ratio of about 3,which is approximately three times amplified than its bias mode.This result agrees well with the previous works based on the BPVE in polar OIHPs and surpasses the results of reported PLDs relying on device geometric anisotropy.Our work opens a new avenue for exploring polar materials with high polarized light sensitivity,thus promoting the development of multi-functional optoelectronic devices.展开更多
基金supported by the National Natural Science Foundation of China(22275117,22575140)the Program of State Key Laboratory of Quantum Optics Technologies and Devices(KF202501)。
文摘Non-covalent interactions play an indispensable role in the construction of molecular ferroelectrics,as they can regulate the relative orientation and stacking mode between molecules.However,the difficulty and challenge lie in precisely designing and regulating the weak intermolecular interactions,ultimately generating macroscopically reversible spontaneous polarization through synergistic effects,thereby achieving ferroelectricity.Herein,we introduced halogenated ammonium Cl-PA^(+)(Cl-PA^(+)is 3-chloropropylaminium)to regulate non-covalent interactions in the structure of hybrid perovskite,and constructed a photoferroelectric semiconductor(Cl-PA)_(2)PbCl_(4)with large piezoelectric coefficient(d_(33)=27.4 pC/N)and high Curie temperature(T_(c)=353 K)through the synergistic effect of hydrogen bonding and halogen-halogen interactions.Compared with non-ferroelectric(PA)_(2)PbCl_(4)(PA^(+)is n-propylaminium),the severe distortion of PbCl_(6)octahedra,weakened N-H…Cl hydrogen bond between organic cations and inorganic frameworks,enhanced C-H…Cl hydrogen bond between cations,and the additional Cl…Cl interaction in the structure synergistically induce the ferroelectricity of(Cl-PA)_(2)PbCl_(4).In addition,the large dipole moment of Cl-PA is also beneficial for constructing molecular ferroelectrics,and the syne rgetic effect of non-covale nt interactions in(Cl-PA)_(2)PbCl_(4)provides the possibility for dipole flipping and symmetry breaking.Therefore,constructing molecular ferroelectrics through the synergistic effect of non-covalent interactions essentially utilizes dynamic coupling and precise equilibrium of multiple weak interactions to achieve the formation,stability,and external field flipping of spontaneous polarization.Through this collaborative design,ferroelectrics with high spontaneous polarization(Ps),low coercive field,and wide temperature range can be achieved,which opens up new directions for flexible electronics and energy storage.
基金supported by the National Key Research and Development Program of China,China(No.2019YFA0210402,2019YFC1805902)Guangdong Science and Technology Program,China(2020B121201003)+1 种基金National Natural Science Foundation of China(52202194,22193042,21833010,21921001,22305105,22201284)the Key Research Program of Frontier Sciences of the Chinese Academy of Sciences(ZDBSLY-SLH024).
文摘Polar two-dimensional organic-inorganic hybrid perovskites(2D-OIHPs)with the bulk photovoltaic effect(BPVE)have shown tremendous potential in developing passive high-performance polarized light detection(PLD)owing to their polarization-driven strong light-matter interaction associated with excellent semiconductor properties.However,the current exploration of these materials for PLD is limited by trial-and-error approaches,which are time-consuming and resource-intensive,highlighting the need for the emergence of polar materials with robust design methods.In this study,we demonstrated the potential of a target-oriented synthesized chiral alternating cation-intercalated(ACI)OIHP,(R-PPA)(EA)PbBr4(1,R-PPA=(R)-(+)-1-phenylpropylamine,and EA=ethylamine),for high-sensitive passive PLD.Under steady illumination,1 exhibits obvious BPVE along the polar direction with a I_(on)/I_(off) ratio of≈103.Additionally,owing to the polarization-driven nature of BPVE,a single crystal device based on 1 exhibited significant angle-resolved short circuit current with a polarization ratio of about 3,which is approximately three times amplified than its bias mode.This result agrees well with the previous works based on the BPVE in polar OIHPs and surpasses the results of reported PLDs relying on device geometric anisotropy.Our work opens a new avenue for exploring polar materials with high polarized light sensitivity,thus promoting the development of multi-functional optoelectronic devices.
