Crystal engineering regulation achieving inverse temperature symmetry breaking ferroelasticity in a cationic displacement type hybrid perovskite system

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.

Simultaneous control of ferromagnetism and ferroelasticity by oxygen octahedral backbone stretching

Coexistence of ferromagnetism and ferroelasticity in a single material is an intriguing phenomenon,but has been rarely found.Here we studied both the ferromagnetism and ferroelasticity in a group of LaCoO3 films with systematically tuned atomic structures.We found that all films exhibit ferroelastic domains with four-fold symmetry and the larger domain size(higher elasticity)is always accompanied by stronger ferromagnetism.We performed synchrotron x-ray diffraction studies to investigate the backbone structure of the CoO6 octahedra,and found that both the ferromagnetism and the elasticity are simultaneously enhanced when the in-plane Co–O–Co bond angles are straightened.Therefore the study demonstrates the inextricable correlation between the ferromagnetism and ferroelasticity mediated through the octahedral backbone structure,which may open up new possibilities to develop multifunctional materials.

Observing ferroelastic switching in Hf_(0.5)Zr_(0.5)O_(2) thin film

Hafnium zirconium oxides(HZO),which exhibit ferroelectric properties,are promising materials for nanoscale device fabrication due to their high complementary metal-oxide-semiconductor(CMOS) compatibility.In addition to piezoelectricity,ferroelectricity,and flexoelectricity,this study reports the observation of ferroelasticity using piezoelectric force microscopy(PFM) and scanning transmission electron microscopy(STEM).The dynamics of 90° ferroelastic domains in HZO thin films are investigated under the influence of an electric field.Switching of the retentive domains is observed through repeated wake-up measurements.This study presents a possibility of enhancing polarization in HZO thin films during wake-up processes.

Ultrahigh-strain ferroelasticity in two-dimensional honeycomb monolayers:from covalent to metallic bonding

We propose a possible ferroelastic switching pathway of two-dimensional(2 D)honeycomb lattice(including graphene,BN,stanene,etc.)that may swap its armchair and zigzag direction,reversing an unprecedented strain of 73.2%.Our ab initio calculations reveal that such pathway cannot work in covalent systems like graphene and BN;for monolayer with metallic bonds like stanene,stanane and In Bi that have all been synthesized,however,such pathway can be feasible with a low switching barrier(<0.15 eV)and stress(<graphene upon 1%tensile strain),also with the highest energy/stress point in the elastic region.Their distinct behaviors are attributed to the different feature of covalent bonds and metallic bonds:the former is rigid with directionality,while the latter is malleable with ductility.A general trend of linear decrease in switching barrier with uprising metallicity for the same group compounds is revealed.Similar behaviors can be extended to bulk zinc-blended or wurtzite structure that can be deemed as multilayer stacking of buckled monolayer.Binary compounds like In Bi monolayer are even multiferroics with both in-plane and vertical ferroelectricity as well as nontrivial topological properties.

The atlas of ferroicity in two-dimensional MGeX_(3) family:Room-temperature ferromagnetic half metals and unexpected ferroelectricity and ferroelasticity

Two-dimensional(2D)ferromagnetic and ferroelectric materials attract unprecedented attention due to the spontaneous-symmetry-breaking induced novel properties and multifarious potential applications.Here we systematically investigate a large family(148)of 2D MGeX3(M=metal elements,X=O/S/Se/Te)by means of the high-throughput first-principles calculations,and focus on their possible ferroic properties including ferromagnetism,ferroelectricity,and ferroelasticity.We discover eight stable 2D ferromagnets including five semiconductors and three half-metals,212D antiferromagnets,and 11 stable 2D ferroelectric semiconductors including two multiferroic materials.Particularly,MnGeSe3 and MnGeTe3 are predicted to be room-temperature 2D ferromagnetic half metals with Tc of 490 and 308 K,respectively.It is probably for the first time that ferroelectricity is uncovered in 2D MGeX3 family,which derives from the spontaneous symmetry breaking induced by unexpected displacements of Ge-Ge atomic pairs,and we also reveal that the electric polarizations are in proportion to the ratio of electronegativity of X and M atoms,and IVB group metal elements are highly favored for 2D ferroelectricity.Magnetic tunnel junction and water-splitting photocatalyst based on 2D ferroic MGeX3 are proposed as examples of wide potential applications.The atlas of ferroicity in 2D MGeX3 materials will spur great interest in experimental studies and would lead to diverse applications.

Multiferroic monolayers VOX(X = Cl, Br, I): Tunable ferromagnetism via charge doping and ferroelastic switching

The fascinating properties arising from the interaction between different ferroic states of two-dimensional(2D) materials have inspired tremendous research interest in the past few years.Under the first-principles calculations,we predict the coexistence of antiferromagnetic and ferroelastic states in VOX(X=Cl,Br,I) monolayers.The results illustrate that the VOX monolayers exhibit indirect bandgap characteristics,i.e.,their gaps decrease with the halide elements changing from Cl to I.The ground states of all these VOX monolayers are antiferromagnetic(AFM) with the magnetic moments contributed by the V 3d electrons.Furthermore,the magnetic ground state changing from AFM to ferromagnetism(FM) can be realized by doping carriers.In addition,the moderate ferroelastic transition barrier and reversible switching signal ensure their high performances of nonvolatile memory devices.Our findings not only offer an ideal platform for investigating the multiferroic properties,but also provide candidate materials for potential applications in spintronics.

A Different Approach to High-Tc Superconductivity: Indication of Filamentary-Chaotic Conductance and Possible Routes to Room Temperature Superconductivity

The empirical relation of between the transition temperature of optimum doped superconductors Tco and the mean cationic charge , a physical paradox, can be recast to strongly support fractal theories of high-Tc superconductors, thereby applying the finding that the optimum hole concentration of σo = 0.229 can be linked with the universal fractal constant δ1 = 8.72109… of the renormalized quadratic Hénon map. The transition temperature obviously increases steeply with a domain structure of ever narrower size, characterized by Fibonacci numbers. However, also conventional BCS superconductors can be scaled with δ1, exemplified through the energy gap relation kBTc ≈ 5Δ0/δ1, suggesting a revision of the entire theory of superconductivity. A low mean cationic charge allows the development of a frustrated nano-sized fractal structure of possibly ferroelastic nature delivering nano-channels for very fast charge transport, in common for both high-Tc superconductor and organic-inorganic halide perovskite solar materials. With this backing superconductivity above room temperature can be conceived for synthetic sandwich structures of less than 2+. For instance, composites of tenorite and cuprite respectively tenorite and CuI (CuBr, CuCl) onto AuCu alloys are proposed. This specification is suggested by previously described filamentary superconductivity of “bulk” CuO1﹣x samples. In addition, cesium substitution in the Tl-1223 compound is an option.

Temperature-dependent Raman spectroscopic study of ferroelastic K_2Sr(MoO_4)

Raman scattering measurements of K_2 Sr（MoO_4）2 were performed in the temperature range of 25–750？C. The Raman spectrum of the low-temperature phase α-K_2 Sr（MoO_4）2 that was obtained by first-principle calculations indicated that the Raman bands in the wavenumber region of 250–500 cm-1 are related to Mo–O bending vibrations in MoO4 tetrahedra,while the Raman bands in the wavenumber region of 650–950 cm-1 are attributed to stretching vibrations of Mo–O bonds.The temperature-dependent Raman spectra reveal that K_2 Sr（MoO_4）2 exhibits two sets of modifications in the Raman spectra at ～ 150？C and ～ 475？C, attributed to structural phase transitions. The large change of the Raman spectra in the temperature range of 150？C to 475？C suggests structural instability of the medium-temperature phase β-K_2 Sr（MoO_4）2.

Organic ferroelastic enantiomers with high Tc and large dielectric switching ratio triggered by order-disorder and displacive phase transition

Molecular-based ferroelastics with dielectric switching properties are highly desirable for their applications on microelectronic dielectric switches,sensors,data storage,and so on.However,the current reports mostly focus on organic-inorganic hybrids containing toxic heavy metal atoms,and the relatively low phase transition temperature limits their application.In this paper,low-toxic organic salt ferroelastic enantiomers(R/S)-4-fluoro-1-azabicyclo[3.2.1]octonium chloride[(R/S)-F-321]were designed and synthesized under the introducing chirality strategy.They undergo a 432F422-type ferroelastic phase transition with a high Curie temperature(Tc)of 470 K,simultaneously exhibiting excellent dielectric switching characteristics.In addition to the ordered-disordered movement of cations,the significant displacement of anions is also responsible for such high Tc and large dielectric switching ratios,which is very rare in molecular-based switching materials.This work enriches the development of molecular ferroelastic switching materials and gives inspiration for the exploration of environmentally friendly high Tc organic salt ferroelastics with prominent switching performances.

Phase field modeling of ferroelastic variant switching in yttria-stabilized t'zirconia with strain gradient elasticity and interface tension

The 6–8 wt%yttria-stabilized zirconia with a tetragonal structure(t’-YSZ)is extensively employed in thermal barrier coatings.The exceptional fracture toughness of t’-YSZ can be attributed to its distinctive ferroelastic toughening mechanism.Microstructure and interface tension play a critical role in ferroelastic variant switching at the micro-and nano-scale.This paper presents an original thermodynamically consistent phase field(PF)theory for analyzing ferroelastic variant switching at the micro-and nano-scale of t’-YSZ.The theory incorporates strain gradient elasticity using higher-order elastic energy and interface tension tensor via geometric nonlinearity to represent biaxial tension resulting from interface energy.Subsequently,a mixed-type formulation is employed to implement the higher-order theory through the finite element method.For an interface in equilibrium,the effects of strain gradient elasticity result in a more uniform distribution of stresses,whereas the presence of interface tension tensor significantly amplifies the stress magnitude at the interface.The introduction of an interface tension tensor increases the maximum value of stress at the interface by a factor of 4 to 10.The nucleation and evolution of variants at a pre-existing crack tip in a mono-phase t’-YSZ have also been studied.The strain gradient elasticity is capable of capturing the size effect of ferroelastic variant switching associated with microstructures in experiments.Specifically,when the grain size approaches that of the specimen,the critical load required for variant switching at the crack tip increases,resulting in greater dissipation of elastic energy during ferroelastic variant switching.Moreover,the interface tension accelerates the evolution of variants.The presented framework exhibits significant potential in modeling ferroelastic variant switching at the micro-and nano-scale.

Molecular Ferroelastic Induced by Mono-/Double-Protonation Strategy

Molecular ferroelastics with the natural features of mechanical flexibility and switchable spontaneous strain have attracted widespread attention in the scientific community due to their potential applications in tunable gratings,flexible memorizers,strain sensors,and intelligent actuators.However,most designs of molecular ferroelastics remain in the stage of blind exploration,posing a challenge to achieve a functional ferroelastic more effectively.Herein,we have successfully obtained a molecular ferroelastic,[Me_(2)NH(CH_(2))_(2)NH_(3)](ReO_(4))_(2)(Me_(2)NH(CH_(2))_(2)NH_(3)=N,N-dimethylethylenediammonium),under the guidance of the mono-/double-protonation strategy.The_double-protonated[Me_(2)NH(CH_(2))_(2)NH_(3)](ReO_(4))_(2) undergoes a paraelastic-ferroelastic phase transition with the Aizu notation of 2/mFi at 322 K.Meanwhile,the theoretical calculation and experimental measurement simultaneously show that[Me_(2)NH(CH_(2))_(2)NH_(3)](ReO_(4))_(2) possesses good mechanical flexibility,because its elastic modulus(E)of 8.26 GPa and hardness(H)of 0.45 GPa are smaller than the average values of organic crystals(E of 12.05 GPa and H of 0.5 GPa),which makes it promising to apply in wearable pressure sensors,implantable medical sensors,high-precision tuners,etc.This work further enriches the molecular ferroelastic family and demonstrates that mono-/double-protonation is one of the effective molecular modification strategies for designing ferroelastics.

Switchable K-O bonds unveiling anomalous ferroelastic transitions in a polar hybrid crystal

Hybrid ferroelastic crystals have garnered considerable interest due to their promising potential as mechanical switches and sensors.The anomalous ferroelastic phase transitions,in which ferroelasticity occurs in the hightemperature phase rather than the low-temperature phase,are of particular interest,but they are sporadically-documented and none of them is involved in breaking of the chemical bonds.Herein,a hydroxyl-containing cation,i.e.,Me_(3)NOH^(+),is employed to construct a three-dimensional hybrid crystal(Me_(3)NOH)_(2)KBiCl_(6)(1).This crystal undergoes distinct twostep structural phase transitions with space-group changes of Pna21–P112_(1)–P63mc,belonging to an anomalous temperaturereversed mm2F2 ferroelastic transition and a normal 6mmF2 ferroelastic transition,respectively.The anomalous ferroelastic transition is entirely driven by switchable K–O coordination bonds involving breaking and reformation.Notably,the dynamic behavior of Me_(3)NOH^(+)cations along with the distortion of inorganic framework enables the manifestation of unusual“high-low-medium”second-harmonic generation-switching behaviors.This study presents the enormous benefits of switchable coordination bonds for inducing anomalous ferroelastic phase transitions,offering valuable insight for the exploration of new multifunctional ferroelastic materials.

Crystal structures and phase transitions in two new hybrid crystals: (Me_(3)NCH_(2)CH_(2)X)_(4)[Ni(NCS)_6](X=Cl and Br)

Understanding phase transitions in multi-component crystals is of importance for regulating specified functional materials.Herein,we present two new organic-inorganic hybrid crystals,(Me_(3)NCH_(2)CH_(2)X)_(4)[Ni(NCS)_6](X=Cl and Br),revealing distinct phase transitions.Specifically,the Clsubstituted cations weakly interact with discrete inorganic part hence reveal step-wise dynamic changes upon heating,which result in multi-step solid-solid phase transitions (P1-P2_1/n-A2/a-Cmce) including a ferroelastic one with a spontaneous strain of 0.0475.Whereas the Br-substituted cations with larger steric effect prevent the solid-solid phase transition but give a solid-liquid phase transition at above 419 K.The present instances well demonstrate the complicity for multi-component crystals arising from the delicate balance established by abundant weak intermolecular interactions,and inspire the design of novel phase-transition materials by judiciously assembling multi-component crystals.

High-entropy ferroelastic(10RE_(0.1))TaO_(4) ceramics with oxygen vacancies and improved thermophysical properties

The primary purpose of this work is to optimize the thermophysical properties of rare-earth tan-talate ceramics using the high-entropy effect.Here,the high-entropy rare-earth tantalate ceramic(Y_(0.1)Nd_(0.1)Sm_(0.1)Gd_(0.1)Dy_(0.1)Ho_(0.1)Er_(0.1)Tm_(0.1)Yb_(0.1)Lu_(0.1))TaO_(4)((10RE_(0.1))TaO_(4))is synthesized successfully.The lat-tice distortion and oxygen vacancy concentration are characterized firstly in the rare-earth tantalates.Notably,compared with single rare-earth tantalates,the thermal conductivity of(10RE_(0.1))TaO_(4) is reduced by 16%-45%at 100℃ and 22%-45%at 800℃,and it also presents lower phonon thermal conductivity in the entire temperature range from 100 to 1200℃.The phonon thermal conductivity(1.0-2.2 W m^(-1) K^(-1),100-1200℃)of(10RE_(0.1))TaO_(4) is lower than that of the currently reported high-entropy four-,five-and six-component rare-earth tantalates.This is the result of scattering by the ferroelastic domain,lattice distortion associated with size and mass disorder,and point defects,which target low-,mid-and high-frequency phonons.Furthermore,(10RE_(0.1))TaO_(4),as an improved candidate for thermal barrier coatings materials(TBCs),has a higher thermal expansion coefficient(10.5×10^(-6)K^(-1) at 1400℃),lower Young’s modulus(123 GPa)and better high-temperature phase stability than that of single rare-earth tantalates.

Ferroelastic phase transitions in three new layered perovskites:(3-XC_(6)H_(5)CH_(2)CH_(2)NH_(3))_(2)[CdCl_(4)](X=F,Cl,and Br)

Two-dimensional organic-inorganic hybrid ferroelastics with high-temperature reversible phase transitions are very rare and have become one of the research hotspots in the field of ferroelastic materials.Herein,we report three new layered organic-inorganic hybrid perovskites based on halogen-substituted phenethylaminium,(3-XC_(6)H_(5)CH_(2)CH_(2)NH_(3))_(2)[CdCl_(4)](X=F(1),CI(2)and Br(3)).They undergo structural phase transitions at 376/371 K,436/430 K,and 421/411 K,respectively,between the isomorphic hightemperature phases(space group I4/mmm,Z=2)and different room-temperature phases with the reduced structural symmetries,i.e.,P21/a(Z=2)in 1,Pi(Z=4)in 2,and P21/a(Z=4)in 3,respectively.These ferroelastic transitions arise from the order-disorder transition of organic cations together with the synchronous displacement of inorganic layers,accompanying with feroelastic spontaneous strains of 0.16,0.13 and 0.12 for 1-3,respectively.By enriching layered perovskite ferroelastics based on halogensubstituted cations,this work provides important clues for exploring new ferroic materials based on hybrid crystals.

厘米级无铅卤化物双钙钛矿单晶实现铁弹性相变触发介电开关性质

在铅基卤化物钙钛矿突破性发展的推动下,卤化物双钙钛矿因其环境友好、丰富的物理化学性能和结构可调性而成为杰出的多用途材料.尽管卤化物双钙钛矿的研究取得了飞速的进展,但在这个吸引人的钙钛矿家族中对可切换电介质的探索仍然很少.本工作通过溶液冷却法成功地生长了单层卤化物双钙钛矿(3-溴丙胺)_(4)AgBiBr_(8)(1)的大尺寸单晶,其尺寸达20 mm×17 mm×5 mm.它经历了由Aizu符号定义的mmm F2/m的铁弹性相变,通过结构分析可知该铁弹相变是八面体畸变和柔性分子运动协同作用的结果.值得注意的是,它在373 K附近具有理想的铁弹性相变触发的可切换电介质性能,可以在两个稳定的电介质状态之间切换.而且,1展现出间接带隙半导体特性和X射线响应,其中在40 V的偏压下1的灵敏度高达517μC Gy_(air)^(-1)cm^(-2).这项工作为具有智能功能的无铅卤化物双钙钛矿提供了一条有效的应用路径.

Revealing the low thermal conductivity of high-entropy rare-earth tantalates via multi-scale defect analysis

Thermal barrier coating(TBC)materials can improve energy conversion efficiency and reduce fossil fuel use.Herein,novel rare earth tantalates RETaO_(4),as promising candidates for TBCs,were reassembled into multi-component solid solutions with a monoclinic structure to further depress thermal conductivity via an entropy strategy.The formation mechanisms of oxygen vacancy defects,dislocations,and ferroelastic domains associated with the thermal conductivity are demonstrated by aberration-corrected scanning transmission electron microscopy.Compared to single-RE RETaO_(4)and 8YSZ,the intrinsic thermal conductivity of(5RE1/5)TaO4 was decreased by 35%–47%and 57%–69%at 1200℃,respectively,which is likely attributed to multi-scale phonon scattering from Umklapp phonon–phonon,point defects,domain structures,and dislocations.r¯3+RE/r5+Ta and low-temperature thermal conductivity are negatively correlated,as are the ratio of elastic modulus to thermal conductivity(E/κ)and high-temperature thermal conductivity.Meanwhile,the high defects’concentration and lattice distortion in high-entropy ceramics enhance the scattering of transverse-wave phonons and reduce the transverse-wave sound velocity,leading to a decrease in the thermal conductivity and Young’s modulus.In addition,5HEC-1 has ultra-low thermal conductivity,moderate thermal expansion coefficients,and high hardness among three five-component high-entropy samples.Thus,5HEC-1 with superior thermal barrier and mechanical properties can be used as promising thermal insulating materials.

Thermal-Induced Ferroelastics in Two Lead-Free Organic-Inorganic Hybrid Perovskites

Lead-based organic-inorganic hybrids occupy a niche in the field of optoelectronics due to exceptional semiconducting properties and potential ferroelasticity.Nevertheless,the possible toxicity of lead restricts their widespread application to a certain extent.Herein,two new lead-free ferroelastic semiconductors are reported:[DMMClEA]_(3)Bi_(2)Br_(9)(compound 1)and[DMMClEA]_(3)Sb_(2)Br_(9)(compound 2)(DMMClEA=N-(chloromethyl)-N,N-dimethylethylammonium),in which the inorganic framework neatly arranges with[Bi_(2)Br_(9)]^(3−)/[Sb_(2)Br_(9)]^(3−)polyhedrons shared by face,forming an A_(3)B_(2)X_(9)-type structure.Both compounds 1 and 2 possess two-step phase transitions,including a3mF2/m-type ferroelastic phase transition,based on the Aizu rule.In addition,dual dielectric switches endow the application toward sensor devices.This finding enriches A_(3)B_(2)X_(9)-type zero-dimensional hybrid ferroelastics and provides an approach to designing high-performance,lead-free perovskite semiconductors with dielectric functionality.

An organic-inorganic hybrid thermochromic ferroelastic with multi-channel switches

Multifunctional switchable materials are attracting tremendous interest because of their great application potential in signal processing,information encryption,and smart devices.Here,we reported an organic-inorganic hybrid thermochromic ferroelastic crystal,[TMIm][CuCl_(4)](TMIm=1,1,3,3-tetramethylimidazolidinium),which undergoes two reversible phase transitions at 333 K and 419 K,respectively.Intriguingly,these three phases experience a remarkable ferroelastic-paraelastic-ferroelastic(2/m-mmm-2/m)transition,which remains relatively unexplored in ferroelastics.Moreover,the ferroelastic domains can be simultaneously switched under temperature and stress stimuli.Meanwhile,[TMIm][CuCl_(4)]exhibits thermochromic phenomenon,endowing it with extra spectral encryption possibilities during information processing.Combined with dielectric switching behavior,[TMIm][Cu Cl_(4)]are promising for practical applications in memory devices,next-generation sensors,and encryption technology.

NH_(+)^(4)/K^(+)-substitution-induced C–F–K coordination bonds for designing the highest-temperature hybrid halide double perovskite ferroelastic

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.