Mixed cation strategy greatly benefits the enhancement of device performance and chemical stability.However,adverse impact also accompanies the mixed cation system simultaneously.It brings the compositional instabilit...Mixed cation strategy greatly benefits the enhancement of device performance and chemical stability.However,adverse impact also accompanies the mixed cation system simultaneously.It brings the compositional instability,wherein the homogeneous film is likely to segregate into multi-phases during the fabrication and ageing process,thus resulting in the efficiency reduction of perovskite solar cells(PSCs)devices.This review focuses on the cation induced phase segregation,and elucidates the segregation mechanisms from the perspectives of film formation and ageing process,respectively.Furthermore,the influence of cation segregation on device performance and operational stability are discussed.And based on these understandings,viable strategies are proposed for the design of phase-stable mixed composition halide perovskites and for suppressing segregation to benefit its development towards commercial applications.展开更多
Ferroelastic hybrid perovskite materials have been revealed the significance in the applications of switches,sensors,actuators,etc.However,it remains a challenge to design high-temperature ferroelastic to meet the req...Ferroelastic hybrid perovskite materials have been revealed the significance in the applications of switches,sensors,actuators,etc.However,it remains a challenge to design high-temperature ferroelastic to meet the requirements for the practical applications.Herein,we reported an one-dimensional organicinorganic hybrid perovskites(OIHP)(3-methylpyrazolium)CdCl_(3)(3-MBCC),which possesses a mmmF2/m ferroelastic phase transition at 263 K.Moreover,utilizing crystal engineering,we replace-CH_(3) with-NH_(2) and-H,which increases the intermolecular force between organic cations and inorganic frameworks.The phase transition temperature of(3-aminopyrazolium)CdCl_(3)(3-ABCC),and(pyrazolium)CdCl_(3)(BCC)increased by 73 K and 10 K,respectively.Particularly,BCC undergoes an unconventional inverse temperature symmetry breaking(ISTB)ferroelastic phase transition around 273 K.Differently,it transforms from a high symmetry low-temperature paraelastic phase(point group 2/m)to a low symmetry high-temperature ferroelastic phase(point group ī)originating from the rare mechanism of displacement of organic cations phase transition.It means that crystal BCC retains in ferroelastic phase above 273 K until melting point(446 K).Furthermore,characteristic ferroelastic domain patterns on crystal BCC are confirmed with polarized optical microscopy.Our study enriches the molecular mechanism of ferroelastics in the family of organic-inorganic hybrids and opens up a new avenue for exploring high-temperature ferroic materials.展开更多
The application of multifunctional materials in various fields such as electronics and signal processors has attracted massive attention. Herein, a new organic-inorganic hybrid material [Et_(3)NCH_(2)Cl]_(2)[MnBr_(4)]...The application of multifunctional materials in various fields such as electronics and signal processors has attracted massive attention. Herein, a new organic-inorganic hybrid material [Et_(3)NCH_(2)Cl]_(2)[MnBr_(4)](1) is reported, which contains two organic amines cations and one [MnBr_(4)] tetrahedral ion. Compound 1 has a dielectric anomaly signal at 338 K, which proves its thermodynamic phase transition. The single crystal measurements at 200 K and 380 K show that the phase transition of compound 1 is caused by the thermal vibration of organic amine cations in the lattice. Moreover, compound 1 shows yellow-green luminescence under UV light irradiation. The magnetism measurements indicate that compound 1 shows switchable magnetic properties. This organic–inorganic material is a multifunctional material with dielectric, optical, and magnetic synergetic switchable effects, which expands a new direction for designing multifunctional materials.展开更多
Ferroelectric semiconductors have sparked growing attention in the field of optoelectronics,due to their unique ferroelectric photovoltaic effect.Recently,substantial efforts have been devoted to the development of fe...Ferroelectric semiconductors have sparked growing attention in the field of optoelectronics,due to their unique ferroelectric photovoltaic effect.Recently,substantial efforts have been devoted to the development of ferroelectric semiconductors,including inorganic oxides,organic-inorganic hybrids,and metal-free perovskites.Nevertheless,reports of ferroelectric semiconductors with a bandgap of less than 2 eV have been scarce.Here,in combination with the incorporation of triiodide(I_(3)−)and the introduction of chiral cations,we successfully constructed a pair of enantiomeric organic-inorganic hybrid ferroelectric semiconductors,(S-1,2-DAP·I)_(4)·I_(3)·BiI_(6)and(R-1,2-DAP·I)_(4)·I_(3)·BiI_(6)(R/S-1,2-DAP=(R/S)-(–)-1,2-diaminopropane),which possess high-temperature multiaxial ferroelectric phase transition with an Aizu notation of 422F2(s)at 405 K,a narrow bandgap of 1.56 eV comparable to that of CH3NH3PbI_(3)(∼1.5 eV),and an impressive piezoelectric response(piezoelectric coefficient,d22 of 35 pC/N)on par with PVDF(polyvinylidene fluoride,30 pC/N).With intriguing attributes,(S-1,2-DAP·I)_(4)·I_(3)·BiI_(6)and(R-1,2-DAP·I)_(4)·I_(3)·BiI_(6)exhibit great potential for application of self-power polarized-light detection and piezoelectric sensors.展开更多
Ferroelastic materials with switchable spontaneous strain possess widely potential applications in the field of energy and information conversion.Recently,organic-inorganic hybrid halide double perovskites (OIHHDPs) h...Ferroelastic materials with switchable spontaneous strain possess widely potential applications in the field of energy and information conversion.Recently,organic-inorganic hybrid halide double perovskites (OIHHDPs) have become a charming new platform for developing various functional materials,such as ferroelectrics,fluorescence and X–ray detection.Nevertheless,OIHHDP ferroelastic materials,especially high-temperature ones,are rare.Herein,we initially synthesized an OIHHDP ferroelastic,(2,2-difluoroethanamine)_(2)[(NH_(4))InCl_6](1),which possesses a ferroelastic phase transition at 407 K.Moreover,thanks to the flexible B-site for OIHHDPs,we replaced the NH_(4)^(+) ions within[(NH_(4))InCl_6]_n^(2n–)formworks with K^(+)ions,which endows with coordination bonds between 2,2-difluoroethanamine organic cations and[KInCl_6]_n^(2n–)formworks.Due to the existence of coordination bonds,the phase transition temperature of (2,2-difluoroethanamine)_(2)[KInCl_6](2) can reach 458 K.As far as we know,this value is the highest reported in OIHHDP ferroelastics.This work offers inspiration for the design of high-temperature OIHHDP phase transition materials including ferroelectrics and ferroelastics.展开更多
To explore the lead-free key scientific issue in perovskite, double perovskite based on Ag Bi and Cu Bi was naturally selected as a competitive candidate due to its fascinating functional features, such as self-powere...To explore the lead-free key scientific issue in perovskite, double perovskite based on Ag Bi and Cu Bi was naturally selected as a competitive candidate due to its fascinating functional features, such as self-powered circularly polarized light detection, X-ray detection, photoluminescence and so on. However, the most challenging point is to simulate the structure and function of traditional lead-based perovskite in new double perovskite. At the same time, there are few suitable double perovskite systems with optical and electrical potential. The above two points greatly limit the competitiveness of double perovskite. In order to solve this problem, firstly, by analyzing and comparing previous studies,we used 2,2-dimethylpropan-1-aminium(abbreviated as 2,2-DPA) as the organic template to assemble materials. Solid-to-solid phase transition materials(2,2-DPA)3Bi2I91 and(2,2-DPA)3Pb2I72 were constructed. Along the path of lead-free and two-dimensional maintenance, we successfully synthesized(2,2-DPA)4AgBiI8.H_(2)O 3 and(2,2-DPA)_(4)CuBiI8.H_(2)O 4. As two typical semiconductors, 3 and 4 with narrower optical band gaps of 1.98 and 1.76 e V show obvious photo-response when the xenon lamp with intensity of 20 m W/cm^(2)is on or off, implying that they may be applied to light-harvesting and light-detecting devices. By referring to the phase transition mechanism of 1 and 2, 3 may be caused by ordered-disordered transition of the organic part, which was proven to be the first solid-to-solid phase transition material with <100>-oriented layered double perovskites with n = 1 by systematic characterization methods after dehydration for all we know. We believed that this work can provide meaningful guidance for the development of lead-free double perovskites.展开更多
Magnet-optical materials embracing coupled magnetic and photoluminescent properties in single phase are promising in microelectronics and optoelectronic devices.However,the current research mainly focuses on tradition...Magnet-optical materials embracing coupled magnetic and photoluminescent properties in single phase are promising in microelectronics and optoelectronic devices.However,the current research mainly focuses on traditional inorganic materials,and there are few reports on molecule materials.Recently,we synthesized an organic–inorganic hybrid complex((C_(6)H_(5)C_(2)H_(3)FNH_(3))_(2)MnCl_(4)(1)with perovskite structure.Physical measurements show that 1 not only behaves as an antiferromagnet with spin canting but also exhibits unusual fluorescent properties.Importantly,under the magnetic field at different temperatures,the luminous intensity of 1 changed,and a red-shift occurred with obviously optical hysteresis.These phenomena directly prove the existence of magneto-optical coupling in 1.More interestingly,the optical hysteresis can be observed in both low and high field,which is unprecedented in other molecular materials.Even in traditional inorganic materials,it can only be observed in strong field.This special function provides the possibility for the application of low energy consumption optoelectronic devices.展开更多
In recent years,it has been found that the flexibility of structure and diversity of the components endow quite an amount of the organic-inorganic hybrid perovskites with novel properties,i.e.,structural phase transit...In recent years,it has been found that the flexibility of structure and diversity of the components endow quite an amount of the organic-inorganic hybrid perovskites with novel properties,i.e.,structural phase transitions.Considering the natural advantage of the perovskite-type structure in generation of stimuliresponsive or smart materials,we synthesized an organic-inorganic hybrid rare-earth double perovskitetype compound,(DMP)_(2) LaRb(NO_(3))_(6)(DMP=N,N-dimethylpyrrolidinium cation,1).It shows reversible phase transition at 219/209 K(heating/cooling).Variable-temperature single-crystal structure analysis and dielectric constant measurements reveal that the thermal vibrations of the polar cation guests and the distortion of the anionic cage-like framework are the origin of the phase transition.Meanwhile,the movement of polar cation in crystal lattices arouses dielectric transition between the low-and highdielectric states,resulting in a switchable property of dielectric constant.The results reveal that the rare-earth double perovskite provides a promising platform for achieving switchable physical/chemical properties.展开更多
基金National Natural Science Foundation of China(22109057,21805010,21975028,52172182,22011540377,22005035)Beijing Municipal Science and Technology Project(Z181100005118002)+2 种基金Beijing Municipal Natural Science Foundation(JQ19008)the China Postdoctoral Science Foundation(Grant No.2020TQ0043,2020M680012)Research Foundation of Jiangxi Educational Committee(GJJ200836).
文摘Mixed cation strategy greatly benefits the enhancement of device performance and chemical stability.However,adverse impact also accompanies the mixed cation system simultaneously.It brings the compositional instability,wherein the homogeneous film is likely to segregate into multi-phases during the fabrication and ageing process,thus resulting in the efficiency reduction of perovskite solar cells(PSCs)devices.This review focuses on the cation induced phase segregation,and elucidates the segregation mechanisms from the perspectives of film formation and ageing process,respectively.Furthermore,the influence of cation segregation on device performance and operational stability are discussed.And based on these understandings,viable strategies are proposed for the design of phase-stable mixed composition halide perovskites and for suppressing segregation to benefit its development towards commercial applications.
基金support from the National Natural Science Foundation of China(No.22175079)support from the National Natural Science Foundation of China(No.22205087)+2 种基金the Open Project Program of Jiangxi Provincial Key Laboratory of Functional Molecular Materials Chemistry,Jiangxi University of Science and Technology(No.20212BCD42018)National Natural Science Foundation of China(No.22275075)Natural Science Foundation of Jiangxi Province(Nos.20204BCJ22015 and 20202ACBL203001).
文摘Ferroelastic hybrid perovskite materials have been revealed the significance in the applications of switches,sensors,actuators,etc.However,it remains a challenge to design high-temperature ferroelastic to meet the requirements for the practical applications.Herein,we reported an one-dimensional organicinorganic hybrid perovskites(OIHP)(3-methylpyrazolium)CdCl_(3)(3-MBCC),which possesses a mmmF2/m ferroelastic phase transition at 263 K.Moreover,utilizing crystal engineering,we replace-CH_(3) with-NH_(2) and-H,which increases the intermolecular force between organic cations and inorganic frameworks.The phase transition temperature of(3-aminopyrazolium)CdCl_(3)(3-ABCC),and(pyrazolium)CdCl_(3)(BCC)increased by 73 K and 10 K,respectively.Particularly,BCC undergoes an unconventional inverse temperature symmetry breaking(ISTB)ferroelastic phase transition around 273 K.Differently,it transforms from a high symmetry low-temperature paraelastic phase(point group 2/m)to a low symmetry high-temperature ferroelastic phase(point group ī)originating from the rare mechanism of displacement of organic cations phase transition.It means that crystal BCC retains in ferroelastic phase above 273 K until melting point(446 K).Furthermore,characteristic ferroelastic domain patterns on crystal BCC are confirmed with polarized optical microscopy.Our study enriches the molecular mechanism of ferroelastics in the family of organic-inorganic hybrids and opens up a new avenue for exploring high-temperature ferroic materials.
基金supported by the the National Natural Science Foundation of China (Nos.21875093, 22161002 and22105089)Natural Science Foundation of Jiangxi Province (Nos.20224BAB214005, 20204BCJ22015 and 20202ACBL203001)Jiangxi Provincial Key Laboratory of Functional Molecular Materials Chemistry (No.20212BCD42018)。
文摘The application of multifunctional materials in various fields such as electronics and signal processors has attracted massive attention. Herein, a new organic-inorganic hybrid material [Et_(3)NCH_(2)Cl]_(2)[MnBr_(4)](1) is reported, which contains two organic amines cations and one [MnBr_(4)] tetrahedral ion. Compound 1 has a dielectric anomaly signal at 338 K, which proves its thermodynamic phase transition. The single crystal measurements at 200 K and 380 K show that the phase transition of compound 1 is caused by the thermal vibration of organic amine cations in the lattice. Moreover, compound 1 shows yellow-green luminescence under UV light irradiation. The magnetism measurements indicate that compound 1 shows switchable magnetic properties. This organic–inorganic material is a multifunctional material with dielectric, optical, and magnetic synergetic switchable effects, which expands a new direction for designing multifunctional materials.
基金This work was supported financially by the National Key Research and Development Program of China(No.2017YFA0204800)National Natural Science Foundation of China(Nos.22175079 and 21875093)+3 种基金Natural Science Foundation of Jiangxi Province(Nos.20204BCJ22015 and 20202ACBL203001)Jiangxi Provincial Department of Education Science and Technology Research Project(No.GJJ210812)Jiangxi Provincial Natural Science Foundation of China(No.20212BAB214021)Science and Technology Project of Jiangxi Provincial Department of Education(No.GJJ200836).
文摘Ferroelectric semiconductors have sparked growing attention in the field of optoelectronics,due to their unique ferroelectric photovoltaic effect.Recently,substantial efforts have been devoted to the development of ferroelectric semiconductors,including inorganic oxides,organic-inorganic hybrids,and metal-free perovskites.Nevertheless,reports of ferroelectric semiconductors with a bandgap of less than 2 eV have been scarce.Here,in combination with the incorporation of triiodide(I_(3)−)and the introduction of chiral cations,we successfully constructed a pair of enantiomeric organic-inorganic hybrid ferroelectric semiconductors,(S-1,2-DAP·I)_(4)·I_(3)·BiI_(6)and(R-1,2-DAP·I)_(4)·I_(3)·BiI_(6)(R/S-1,2-DAP=(R/S)-(–)-1,2-diaminopropane),which possess high-temperature multiaxial ferroelectric phase transition with an Aizu notation of 422F2(s)at 405 K,a narrow bandgap of 1.56 eV comparable to that of CH3NH3PbI_(3)(∼1.5 eV),and an impressive piezoelectric response(piezoelectric coefficient,d22 of 35 pC/N)on par with PVDF(polyvinylidene fluoride,30 pC/N).With intriguing attributes,(S-1,2-DAP·I)_(4)·I_(3)·BiI_(6)and(R-1,2-DAP·I)_(4)·I_(3)·BiI_(6)exhibit great potential for application of self-power polarized-light detection and piezoelectric sensors.
基金supported financially by the National Key Research and Development Program of China (No. 2017YFA0204800)National Natural Science Foundation of China (Nos. 22175079 and 21875093)+1 种基金Natural Science Foundation of Jiangxi Province (Nos. 20204BCJ22015 and 20202ACBL203001)Jiangxi Provincial Department of Education Science and Technology Research Project (No. GJJ210812)。
文摘Ferroelastic materials with switchable spontaneous strain possess widely potential applications in the field of energy and information conversion.Recently,organic-inorganic hybrid halide double perovskites (OIHHDPs) have become a charming new platform for developing various functional materials,such as ferroelectrics,fluorescence and X–ray detection.Nevertheless,OIHHDP ferroelastic materials,especially high-temperature ones,are rare.Herein,we initially synthesized an OIHHDP ferroelastic,(2,2-difluoroethanamine)_(2)[(NH_(4))InCl_6](1),which possesses a ferroelastic phase transition at 407 K.Moreover,thanks to the flexible B-site for OIHHDPs,we replaced the NH_(4)^(+) ions within[(NH_(4))InCl_6]_n^(2n–)formworks with K^(+)ions,which endows with coordination bonds between 2,2-difluoroethanamine organic cations and[KInCl_6]_n^(2n–)formworks.Due to the existence of coordination bonds,the phase transition temperature of (2,2-difluoroethanamine)_(2)[KInCl_6](2) can reach 458 K.As far as we know,this value is the highest reported in OIHHDP ferroelastics.This work offers inspiration for the design of high-temperature OIHHDP phase transition materials including ferroelectrics and ferroelastics.
基金financially supported by the National Natural Science Foundation of China (No. 21991141)。
文摘To explore the lead-free key scientific issue in perovskite, double perovskite based on Ag Bi and Cu Bi was naturally selected as a competitive candidate due to its fascinating functional features, such as self-powered circularly polarized light detection, X-ray detection, photoluminescence and so on. However, the most challenging point is to simulate the structure and function of traditional lead-based perovskite in new double perovskite. At the same time, there are few suitable double perovskite systems with optical and electrical potential. The above two points greatly limit the competitiveness of double perovskite. In order to solve this problem, firstly, by analyzing and comparing previous studies,we used 2,2-dimethylpropan-1-aminium(abbreviated as 2,2-DPA) as the organic template to assemble materials. Solid-to-solid phase transition materials(2,2-DPA)3Bi2I91 and(2,2-DPA)3Pb2I72 were constructed. Along the path of lead-free and two-dimensional maintenance, we successfully synthesized(2,2-DPA)4AgBiI8.H_(2)O 3 and(2,2-DPA)_(4)CuBiI8.H_(2)O 4. As two typical semiconductors, 3 and 4 with narrower optical band gaps of 1.98 and 1.76 e V show obvious photo-response when the xenon lamp with intensity of 20 m W/cm^(2)is on or off, implying that they may be applied to light-harvesting and light-detecting devices. By referring to the phase transition mechanism of 1 and 2, 3 may be caused by ordered-disordered transition of the organic part, which was proven to be the first solid-to-solid phase transition material with <100>-oriented layered double perovskites with n = 1 by systematic characterization methods after dehydration for all we know. We believed that this work can provide meaningful guidance for the development of lead-free double perovskites.
基金National Key Research and Development Program of China,Grant/Award Numbers:2018YFA0306004,2017YFA0204800National Natural Science Foundation of China,Grant/Award Numbers:21973038,21805119,12064002,21875093,22105089,61904119,11974126+4 种基金The Joint Fund for Regional Innovation and Development,Grant/Award Number:U20A2073Natural Science Foundation of Jiangxi Province,Grant/Award Numbers:20204BCJ22015,20202ACBL203001Natural Science Foundation of the Jiangsu Higher Education Institutions of China(,Grant/Award Number:20KJB140019)Jiangxi Provincial Key Laboratory of Functional Molecular Materials Chemistry,Grant/Award Number:20212BCD42018Interdisciplinary program of Wuhan National High Magnetic Field Center,Grant/Award Number:WHMFC202133。
文摘Magnet-optical materials embracing coupled magnetic and photoluminescent properties in single phase are promising in microelectronics and optoelectronic devices.However,the current research mainly focuses on traditional inorganic materials,and there are few reports on molecule materials.Recently,we synthesized an organic–inorganic hybrid complex((C_(6)H_(5)C_(2)H_(3)FNH_(3))_(2)MnCl_(4)(1)with perovskite structure.Physical measurements show that 1 not only behaves as an antiferromagnet with spin canting but also exhibits unusual fluorescent properties.Importantly,under the magnetic field at different temperatures,the luminous intensity of 1 changed,and a red-shift occurred with obviously optical hysteresis.These phenomena directly prove the existence of magneto-optical coupling in 1.More interestingly,the optical hysteresis can be observed in both low and high field,which is unprecedented in other molecular materials.Even in traditional inorganic materials,it can only be observed in strong field.This special function provides the possibility for the application of low energy consumption optoelectronic devices.
基金Project supported by the National Natural Science Foundation of China(21805119,21875093)Youth Science Foundation of Jiangxi Provincial Office of Science and Technology(20192ACBL21010)Natural Science Foundation of Jiangxi Province(20204BCJ22015,20202ACBL203001)。
文摘In recent years,it has been found that the flexibility of structure and diversity of the components endow quite an amount of the organic-inorganic hybrid perovskites with novel properties,i.e.,structural phase transitions.Considering the natural advantage of the perovskite-type structure in generation of stimuliresponsive or smart materials,we synthesized an organic-inorganic hybrid rare-earth double perovskitetype compound,(DMP)_(2) LaRb(NO_(3))_(6)(DMP=N,N-dimethylpyrrolidinium cation,1).It shows reversible phase transition at 219/209 K(heating/cooling).Variable-temperature single-crystal structure analysis and dielectric constant measurements reveal that the thermal vibrations of the polar cation guests and the distortion of the anionic cage-like framework are the origin of the phase transition.Meanwhile,the movement of polar cation in crystal lattices arouses dielectric transition between the low-and highdielectric states,resulting in a switchable property of dielectric constant.The results reveal that the rare-earth double perovskite provides a promising platform for achieving switchable physical/chemical properties.