Intergrowth ferroelectric semiconductors with excellent spontaneous polarization field are highly promising piezo-photocatalytic candidate materials.In addition,developing structural design and revealing polarization ...Intergrowth ferroelectric semiconductors with excellent spontaneous polarization field are highly promising piezo-photocatalytic candidate materials.In addition,developing structural design and revealing polarization enhancement in-depth mechanism are top priorities.Herein,we introduce the intergrowth ferroelectrics Bi_(7)Ti_(4)NbO_(21)thin-layer nanosheets for piezo-photocatalytic CO_(2)reduction.Density functional theory(DFT)calculations indicate that interlayer lattice mismatch leads to increased tilting and rotation angle of Ti/NbO_(6)octahedra on perovskite-like layers,serving as the main reason for increased polarization.Furthermore,the tilting and rotation angle of the interlayer octahedron further increase under stress,suggesting a stronger driving force generated to facilitate charge carrier separation efficiency.Meanwhile,Bi_(7)Ti_(4)NbO_(21)nanosheets provide abundant active sites to effectively adsorb CO_(2)and acquire sensitive stress response,thereby presenting synergistically advanced piezo-photocatalytic CO_(2)reduction activity with a high CO generation rate of 426.97μmol g^(-1)h^(-1).Our work offers new perspectives and directions for initiating and investigating the mechanisms of high-performance intergrowth piezo-photocatalysts.展开更多
Doped HfO_(2)as an emerging ferroelectric material,holds considerable promise for non-volatile memory applications.Epitaxial growth of doped HfO_(2)thin films is widely adopted as an effective technique for revealing ...Doped HfO_(2)as an emerging ferroelectric material,holds considerable promise for non-volatile memory applications.Epitaxial growth of doped HfO_(2)thin films is widely adopted as an effective technique for revealing the intrinsic ferroelectric properties.In this study,based on systematic structural,chemical and electrical investigations,the influences of Mn doping and substrate orientation on ferroelectric properties of Mn-doped HfO_(2)epitaxial thin films are investigated.The results demonstrate that Mn-doped HfO_(2)thin films with orthorhombic phase can be epitaxially grown along[111]out-of-plane direction on both SrTiO_(3)(001)and(110)substrates,and 10%Mn-doping significantly stabilizes the orthorhombic polar phase and enhances the ferroelectric polarization.Interestingly,compared to the films on SrTiO_(3)(001)substrate,the better crystallinity and reduction of oxygen vacancy amount in Mn-doped HfO_(2)films grown on the SrTiO_(3)(110)substrate are observed,which enhance the remanent polarization and reduce the coercive field.It provides an effective approach for the controllable regulation of defects and the enhancement of intrinsic ferroelectricity in HfO_(2)-based materials.展开更多
基金support from the Natural Science Foundation of Jiangsu Province(BK20220596)Innovative science and technology platform project of cooperation between Yangzhou City and Yangzhou University,China(No.YZ202026305)+1 种基金Natural Science Foundation of China(21922202,21673202 and 22272147)the Priority Academic Program Development of Jiangsu Higher Education Institutions.
文摘Intergrowth ferroelectric semiconductors with excellent spontaneous polarization field are highly promising piezo-photocatalytic candidate materials.In addition,developing structural design and revealing polarization enhancement in-depth mechanism are top priorities.Herein,we introduce the intergrowth ferroelectrics Bi_(7)Ti_(4)NbO_(21)thin-layer nanosheets for piezo-photocatalytic CO_(2)reduction.Density functional theory(DFT)calculations indicate that interlayer lattice mismatch leads to increased tilting and rotation angle of Ti/NbO_(6)octahedra on perovskite-like layers,serving as the main reason for increased polarization.Furthermore,the tilting and rotation angle of the interlayer octahedron further increase under stress,suggesting a stronger driving force generated to facilitate charge carrier separation efficiency.Meanwhile,Bi_(7)Ti_(4)NbO_(21)nanosheets provide abundant active sites to effectively adsorb CO_(2)and acquire sensitive stress response,thereby presenting synergistically advanced piezo-photocatalytic CO_(2)reduction activity with a high CO generation rate of 426.97μmol g^(-1)h^(-1).Our work offers new perspectives and directions for initiating and investigating the mechanisms of high-performance intergrowth piezo-photocatalysts.
基金supported by the National Natural Science Foundation of China(Grant Nos.52125204,52250281,52422209,92163210,and U21A2066)the Na-tional Key Research and Development Program of China(Grant Nos.2024YFA1208601,2022YFB3807602,and 2022YFB3807604).
文摘Doped HfO_(2)as an emerging ferroelectric material,holds considerable promise for non-volatile memory applications.Epitaxial growth of doped HfO_(2)thin films is widely adopted as an effective technique for revealing the intrinsic ferroelectric properties.In this study,based on systematic structural,chemical and electrical investigations,the influences of Mn doping and substrate orientation on ferroelectric properties of Mn-doped HfO_(2)epitaxial thin films are investigated.The results demonstrate that Mn-doped HfO_(2)thin films with orthorhombic phase can be epitaxially grown along[111]out-of-plane direction on both SrTiO_(3)(001)and(110)substrates,and 10%Mn-doping significantly stabilizes the orthorhombic polar phase and enhances the ferroelectric polarization.Interestingly,compared to the films on SrTiO_(3)(001)substrate,the better crystallinity and reduction of oxygen vacancy amount in Mn-doped HfO_(2)films grown on the SrTiO_(3)(110)substrate are observed,which enhance the remanent polarization and reduce the coercive field.It provides an effective approach for the controllable regulation of defects and the enhancement of intrinsic ferroelectricity in HfO_(2)-based materials.