Ferroelastic Phase Transition Research Articles

Phase Transitions and Nonlinear Optical Property Modifications in BaGa4Se7.

Phase transitions can change the crystal structure and modify the physical properties of crystals. In this work, we investigate the phase transition behavior in BaGa4Se7, an important middle infrared (mid-IR) nonlinear optical (NLO) crystal, in the temperature range from room temperature to 1173 K. Interestingly, the BaGa4Se7 crystal undergoes a reversible ferroelastic phase transition at T = 528 K, resulting in the presence of a newly discovered phase (γ-phase) at the higher temperature. The experimental temperature dependence of optical birefringence, as well as the first-principles birefringence and NLO coefficients, reveals that the γ-phase exhibits larger birefringence and better NLO properties compared with those of the low-temperature phase (α-phase). This work demonstrates that phase-transition-induced structural modification can improve the mid-IR NLO properties, which would provide an effective avenue to obtain materials with good optoelectronic performance.

Three-Step Ferroelastic Transitions from Hexagonal to Triclinic Phases in a Hybrid Perovskite: (1-Fluoromethyl-1-methylpyrrolidine)[CdCl3

Hybrid ferroelastic crystals have emerged as a hot research topic in recent years owing to their prospective applications in piezoelectric sensors, mechanical switches, and optoelectronic devices. Nevertheless, most of the documented materials exhibit one-step or two-step ferroelastic phase transition(s), and those with multistep ferroelastic transitions are extremely scarce. We present a new hexagonal molecular perovskite based on a fluoro-substituted flexible cyclic ammonium cation, (1-fluoromethyl-1-methylpyrrolidine)[CdCl3] (1), undergoing unusual three-step ferroelastic phase transitions from hexagonal paraelastic phase to orthorhombic, monoclinic, and triclinic ferroelastic phases at 388, 376, and 311 K, respectively, with Aizu notation of 6/mmmFmmm, mmmF2/m, and 2/mF-1, featuring spontaneous strain of 0.002, 0.023, and 0.110, respectively. Furthermore, variable-temperature single-crystal diffraction reveals that the phase-transition mechanism in 1 principally originates from intriguing dynamic change of organic cations and synchronous displacement of inorganic chains. This scarce instance of multistep hybrid ferroelastic provides important clues for finding advanced ferroelastic materials.

A High Working Temperature Multiferroic Induced by Inverse Temperature Symmetry Breaking.

Molecular-based multiferroic materials that possess ferroelectric and ferroelastic orders simultaneously have attracted tremendous attention for their potential applications in multiple-state memory devices, molecular switches, and information storage systems. However, it is still a great challenge to effectively construct novel molecular-based multiferroic materials with multifunctionalities. Generally, the structure of these materials possess high symmetry at high temperatures, while processing an obvious order-disorder or displacement-type ferroelastic or ferroelectric phase transition triggered by symmetry breaking during the cooling processes. Therefore, these materials can only function below the Curie temperature (Tc), the low of which is a severe impediment to their practical application. Despite great efforts to elevate Tc, designing single-phase crystalline materials that exhibit multiferroic orders above room temperature remains a challenge. Here, an inverse temperature symmetry-breaking phenomenon was achieved in [FPM][Fe3(μ3-O)(μ-O2CH)8] (FPM stands for 3-(3-formylamino-propyl)-3,4,5,6-tetrahydropyrimidin-1-ium, which acts as the counterions and the rotor component in the network), enabling a ferroelastoelectric phase at a temperature higher than Tc (365 K). Upon heating from room temperature, two-step distinct symmetry breaking with the mm2Fm species leads to the coexistence of ferroelasticity and ferroelectricity in the temperature interval of 365-426 K. In the first step, the FPM cations undergo a conformational flip-induced inverse temperature symmetry breaking; in the second step, a typical ordered-disordered motion-induced symmetry breaking phase transition can be observed, and the abnormal inverse temperature symmetry breaking is unprecedented. Except for the multistep ferroelectric and ferroelastic switching, this complex also exhibits fascinating nonlinear optical switching properties. These discoveries not only signify an important step in designing novel molecular-based multiferroic materials with high working temperatures, but also inspire their multifunctional applications such as multistep switches.

A Sn-Based Hybrid Ferroelastic Semiconductor with High-Temperature Dielectric Switching.

Organic-inorganic halide hybrids have been extensively developed and used in optoelectronic devices because of their superior performance such as ease of assembly, flexible structural tunability, and excellent optoelectronic properties. Ferroelastic strain might be used to modulate and control photoelectric properties such as photovoltaic voltage, while organic-inorganic hybrid ferroelastic semiconductors remain relatively unexplored. Herein, we successfully design a new Sn-base, lead-free hybrid ferroelastic semiconductor, [TPMA]2[SnCl6] (TPMA = benzyl trimethylammonium). It undergoes a high-temperature -3mF-1-type ferroelastic phase transition at 408 K, and intriguingly, its ferroelastic domains can be simultaneously switched under the stimulation of external heat and stress. The ferroelastic phase transition might be derived from the order-disorder transition of organic cations during heating and cooling. Moreover, [TPMA]2[SnCl6] also demonstrates a high-temperature dielectric switching property around 408 K, which has good stability and reproducibility. With those benefits, [TPMA]2[SnCl6] shows great potential in applications such as energy storage devices, optoelectronic devices, shape memory, intelligent switches, and so on.

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.

Thermally Reversible Luminescence in Ferroelastic Phase Transition Materials

AbstractThe thermally reversible luminescent materials with information encryption are important and widely used in the information age. However, it is challenging to obtain such materials. In this work, a 0D In‐based hybrid compound [(CH3)3NCH2CHCH2]2InCl5 ((TAMAC)2InCl5) is synthesized and undergoes a high‐temperature ferroelastic phase transition with an Aizu notation of mmF2/m at 333 K. In the room temperature phase (RTP), it shows a weak blue glow with a photoluminescent quantum yield (PLQY) of 0.32% under the UV lamp at 365 nm. By using a metal ion doping strategy to improve the photophysical properties, a series of compounds is obtained: (TAMAC)2In1‐xCl5:xSb3+ (x = 0.1%,0.5%,1%, and 1.5%, x represents the actual amount) with the same ferroelastic phase transition as that found in (TAMAC)2InCl5. When x = 0.5%, the PLQY reaches 50.66% with the luminous color change from blue to orange. Interestingly, it is found that the orange luminescence of the doped materials can rapidly and reversibly quench and recover between heating and cooling cycles, where the thermally induced phase transition results in this thermally reversible luminescence phenomenon. This discovery reveals the mechanism of luminescence quenching and phase transition, and provides a new pathway for the construction of new thermal‐sensitive luminescent materials with information encryption.

Crystal structure and microwave dielectric properties of A- and B-site co-substituted NdNbO4 ceramics

The microwave dielectric properties of NdNbO4 (NN) ceramics were optimized by substituting Ca2+ at the A-site and W6+ at the B-site. (1-x)NdNbO4-xCaWO4 (NNCWx) (x = 0–0.3) ceramics crystallize in the monoclinic fergusonite structure (space group I2/a), whereas NNCW-0.4 exhibits a tetragonal scheelite structure (space group I41/a), suggesting that Ca2+/W6+ doping effectively contributed to the ferroelastic phase transition. A near-zero temperature coefficient of resonant frequency (τf) of +7.8 ppm/°C, a high Q×f value of 59,190 GHz, and a low permittivity (εr) of 17.51 were obtained for the NNCW-0.3 ceramic. With the increase of x, the permittivity decreases gradually, while τf shows the opposite trend. The permittivity is mainly affected by the polarizability per unit molar volume (α/Vm) and the rattling effect of A-site cations (Nd3+ and Ca2+). The Q×f values of NNCWx ceramics are mainly affected by relative density, packing fraction, and lattice energy (U). The influencing mechanism of τf is a combination of an increase in the temperature coefficient of ion polarizability (ταm), lattice strain, and phase transition.

Ferroelastic rare‐earth tantalates for multifunctional thermal/environmental barrier coatings: A perspective

AbstractThis perspective outlines the research directions of ferroelastic rare‐earth (RE) tantalates (RETaO4), which have been studied as multifunctional thermal/environmental barrier coatings (T/EBCs) with working temperatures above 1600°C. Ferroelastic RETaO4 ceramics exhibit several distinct features, including the reversible second‐order ferroelastic phase transition, high toughness, low thermal conductivity, low oxygen ion conductivity, and adjustable thermal expansion coefficients. This perspective provides a concise summary of the research progress on tantalate coatings synthesized via air plasma spraying and electron beam physical vapor deposition. The service performance of tantalate coatings is typically evaluated through thermal fatigue and shock measurements. Uncovering the failure mechanisms and understanding influencing factors are key aspects for future studies. In this regard, establishing the synthesis‐structure‐property relationship of RETaO4 coatings is essential. This brief perspective can serve as a guide for future work on RETaO4 coatings and further advancements in their applications across various fields, including aviation engines and gas turbines.

High-Temperature Ferroelasticity and Photoluminescence in a 2D Monolayer Perovskite Compound: (C5NH8Br)2PbBr4.

Hybrid organic-inorganic perovskites (HOIPs) have attracted much attention due to their excellent properties and easy synthesis. As far as we know, most documented ferroelastics mainly focus on the 3D (three-dimensional) perovskites, the 2D monolayer perovskite ferroelastics are rarely reported before. In this work, we synthesized a 2D lead-based perovskite (C5NH13Br)2PbBr4 (1) (C5NH13Br = 5-bromoamylamine cation) by introducing flexible chain organic cations. The evolution of ferroelastic domains observed by a polarized light microscope confirms that compound 1 undergoes a ferroelastic phase transition at 392/384 K. In addition, its direct band gap is 2.877 eV. Interestingly, the material emits an attractive blue light (quantum yield 5.06%) under UV light. Three structural descriptors are introduced to quantitatively analyze the relationship between structural distortion and the shape of emission peak. This work provides a way to design multifunctional perovskite-type materials.

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 organic-inorganic hybrid perovskites (OIHP) (3-methylpyrazolium)CdCl3 (3-MBCC), which possesses a mmmF2/m ferroelastic phase transition at 263 K. Moreover, utilizing crystal engineering, we replace ‒CH3 with ‒NH2 and ‒H, which increases the intermolecular force between organic cations and inorganic frameworks. The phase transition temperature of (3-aminopyrazolium)CdCl3 (3-ABCC), and (pyrazolium)CdCl3 (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 1¯) 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.

Characteristics of ferroelastic domains and thermal transport limits in HfO2 alloying YTaO4 ceramics

Low thermal conductivity and a ferroelastic tetragonal-monoclinic phase transition are essential for the use of YTaO4 in thermal barrier coatings. The phonon scattering mechanism of HfO2 alloying YTaO4 is elucidated via the analysis of microstructural characteristics, and a limit thermal conductivity (1.3 W·m−1·K−1) is achieved. Furthermore, a revised model is developed to successfully derive high-temperature phonon thermal conductivity, showing a decrease in the phonon scattering coefficient as strain field fluctuations decrease. This proves that the phonon scattering coefficient is temperature dependent. Atomic weight disorder plays a significant role in thermal conductivity reduction, whereas HfO2 alloying enhances lattice symmetry and weakens the phonon scattering, and thus mitigates thermal conductivity reduction. Additionally, domain boundary width and spacing mismatch between neighboring domains cause the scattering of phonons and further reduce the thermal conductivity. Finally, evidence of a diffusive domain boundary validates that tetragonal-monoclinic transition is a second-order process.

First-principles study of ferroelectricity, antiferroelectricity, and ferroelasticity in two-dimensional γ -AlOOH

The exploration of two-dimensional (2D) ferroic materials and the investigation of ferroic couplings are highly desired in view of the design of next-generation functional devices. Herein, we report through first-principles calculations that the single-layer \ensuremath{\gamma}-AlOOH exhibits intrinsic ferroelectric (FE), antiferroelectric (AFE), and ferroelastic properties. The polarization and antipolarization originate from the orientational displacements of hydrogen atoms actuated by two soft phonon modes of the centrosymmetric phase. We studied a possible FE switching process and the FE-AFE transformation in the cases of monolayer and bulk, resulting in the prediction of a stable bulk AFE phase with similar energy to the FE ground state. Moreover, the \ensuremath{\gamma}-AlOOH monolayer shows a giant ferroelastic phase transition capable of efficiently tuning the ferroelectricity, which is able to accomplish a 90 \ifmmode^\circ\else\textdegree\fi{} switching of polarization and leads to an FE/AFE quadruple state. Our work adds a unique candidate to the family of 2D ferroics, broadening the platform for the design of ferroic-based devices.

Templating Influence of Regulated Inorganic Framework in Two-Dimensional Ferroelastic Perovskites: (C3 H5 CH2 NH3 )2 [MCl4 ] (M=Mn and Cd).

The remarkable material stability and structural diversity of two-dimensional (2D) organic-inorganic hybrid perovskites (OIHPs) constitute a vast available library of versatile materials. In particular, ferroelastic property, for which the spontaneous strain can be transformed by applying mechanical stress, is very promising for extensive nanotechnological applications. However, integrating ferroelastic property into 2D OIHPs is still in its infancy. Herein, we designed two new 2D OIHPs (C3 H5 CH2 NH3 )2 [MCl4 ] (M=Mn for 1 and Cd for 2), which undergo reversible ferroelastic phase transitions with an Aizu expression 4/mmmFmmm. The templating influence of the more distorted inorganic framework on the disordering of organic cations and the stronger hydrogen bonds has a key role in the striking improvement of Curie temperature from 246 K in 1 to 273 K in 2. Meanwhile, the minimized alteration of structural motif ensures the well maintaining of the ferroelastic performance in the forms of crystals and thin films, as demonstrated by the identifiable evolution of domain structures. This work will provide a fertile new ground for enlarging the limited number of 2D ferroelastic OIHPs with better practical utility.

Influence of Pd(II) Adsorption on High-Temperature Ferroelastic Phase Transition in (2-Amino-2-thiazolinium)PbBr3.

Ferroelastic materials have received special attention because of their great promise for mechanical switches, piezoelectric sensors, and data storage applications. Here, we report a novel ferroelastic semiconducting hybrid organic-inorganic perovskite (C3H7N2S)PbBr3 (1) [(C3H7N2S)+ is 2-amino-2-thiazolinium] with a ferroelastic phase transition at 395 K and an optical band gap of 3.43 eV. 1 has a one-dimensional BaNiO3-type structure and undergoes a high-temperature ferroelastic phase transition with an Aizu notation of mmmF2/m. Meanwhile, 1 exhibits dielectric switch near the phase transition temperature. By introducing the thioether group, the motion of the molecules or ions of 1 is hindered after the sorption of Pd(II) metal ions, which leads to the disappearance of the high-temperature ferroelastic phase transition and dielectric switch. This is the first reported ferroelastic semiconductor material with Pd(II) adsorption property, by studying the influence of Pd(II) adsorption on high-temperature ferroelastic phase transition, it may be enlightening to further uncover the mechanism of phase transition or the origin of ferroelasticity, which represents an important step toward multifunctional applications of lead-hybrid perovskite-based ferroelastic materials.

An anomalous ferroelastic phase transition arising from an unusual cis-/anti-conformational reversal of polar organic cations.

Hybrid ferroelastics have attracted increasing attention for their potential application as mechanical switches. The sporadically documented anomalous ferroelastic phase transitions, i.e., ferroelasticity that appears at a high-temperature phase rather than a low-temperature phase, are of particular interest but are not well understood at the molecular level. By judiciously choosing a polar and flexible organic cation (Me2NH(CH2)2Br+) with cis-/anti- conformations as an A-site component, we obtained two new polar hybrid ferroelastics, A2[MBr6] (M = Te for 1 and Sn for 2). These materials undergo distinct thermal-induced ferroelastic phase transitions. The larger [TeBr6]2- anions anchor the adjacent organic cations well and essentially endow 1 with a conventional ferroelastic transition (P21 → Pm21n) arising from a common order-disorder transition of organic cations without conformational changes. Moreover, the smaller [SnBr6]2- anions can interact with the adjacent organic cations in energetically similar sets of intermolecular interactions, enabling 2 to undergo an anomalous ferroelastic phase transition (P212121 → P21) arising from an unusual cis-/anti-conformational reversal of organic cations. These two instances demonstrate the importance of the delicate balance of intermolecular interactions for inducing anomalous ferroelastic phase transitions. The findings here provide important insights for seeking new multifunctional ferroelastic materials.

Strong spin-lattice entanglement in cobaltites

Strongly correlated electronic system contains strong coupling among multi-order parameters and is easy to efficiently tune by external field. Cobaltite (LaCoO<sub>3</sub>) is a typical multiferroic (ferroelastic and ferromagnetic) material, which has been extensively investigated over decades. Conventional research on cobaltites has focused on the ferroelastic phase transition and structure modulation under stress. Recently, researchers have discovered that cobaltite thin films undergo a paramagnetic-to-ferromagnetic phase transition under tensile strain, however, its origin has been controversial over decades. Some experimental evidence shows that stress leads the valence state of cobalt ions to decrease, and thus producing spin state transition. Other researchers believe that the stress-induced nano-domain structure will present a long-range ordered arrangement of high spin states, which is the main reason for producing the ferromagnetism of cobalt oxide films. In this paper, we review a series of recent researches of the strong correlation between spin and lattice degrees of freedom in cobalt oxide thin films and heterojunctions. The reversible spin state transition in cobalt oxide film is induced by structural factors such as thin-film thickness, lattice mismatch stress, crystal symmetry, surface morphology, interfacial oxygen ion coordination, and oxygen octahedral tilting while the valence state of cobalt ions is kept unchanged, and thus forming highly adjustable macroscopic magnetism. Furthermore, the atomic-level precision controllable film growth technology is utilized to construct single cell layer cobaltite superlattices, thereby achieving ultra-thin two-dimensional magnetic oxide materials through efficient structure regulation. These advances not only clarified the strong coupling between lattice and spin order parameters in the strongly correlated electronic system, but also provided excellent candidate for the realization of ultra-thin room temperature ferromagnets that are required by oxide spintronic devices.

Ferroelastic phase transition and the role of volume strain in the structural trapping of a metastable quenched low-spin high-symmetry phase in [Ru0.35Fe0.65(ptz)6](BF4)2

Spin-crossover materials exhibit thermal conversion of their electronic state from low to high spin, involving both intra- and inter-molecular structural reorganisations, eventually accompanied by symmetry breaking, within the crystal.

Methyl regulation triggers high-temperature ferroelastic phase transition.

The multifunctional tuning of solid-state dielectric switches constructed from organic-inorganic hybrid materials (OIHMs) has received great attention. In particular, molecular ferroelastics with dielectric phase transitions have considerable potential in the optical and electrical fields owing to their adjustable structures and physical features. However, it remains a challenge to effectively design ferroelastics with high phase transition temperature (Tc). We used [TTMA]2CdI4 (TTMA = tetramethylammonium, 1) as a template to continuously increase the molecular weight and change the structure of the hybrid material by modifying and extending the alkane chain in the cation. Therefore, a series of OIHMs were eventually developed: [TMEA]2CdI4 (TMEA = trimethylethylammonium, 2), [TMPA]2CdI4 (TMPA = trimethylpropylammonium, 3), and [TMIPA]2CdI4 (TMIPA = trimethyliso-propylammonium, 4). Among them, the Tc of ferroelastic 3 increased up to 387 K. DSC and temperature-related dielectric constant tests prove the occurrence of the phase transition for 1, 2, and 3. The structures further indicate that the phase transition is caused by the order-disorder cation motion. The extension of the alkyl chain greatly increases Tc and endows 3 with ferroelasticity at room temperature.

Improper ferroelastic phase transition in a hydrogen-bonded metallocyanide-based (azetidinium)2(H3O)[Co(CN)6] framework.

A hydrogen-bonded metallocyanide-based (AZE)2(H3O)[Co(CN)6] framework was obtained by introducing a hydronium cation to the A2B(1)B(2)CN6-type structure. Simple K+/H3O+ substitution exchange the three-dimensional structure of the double-perovskite into two-dimensional layers containing open inorganic cages with a strongly discontinuous improper ferroelastic phase transition.

A photoluminescent chiral lead-free hybrid ferroelastic semiconductor with switchable second-harmonic generation.

Chiral organic-inorganic hybrid semiconductors (COIHSs) dominated by lead halides have recently gained tremendous interest. Here, we report a lead-free photoluminescent COIHS [R-3-hydroxylpiperidinium]2SbCl5 with a bandgap of 3.14 eV. It shows a ferroelastic phase transition at 341 K accompanied by a switchable second-harmonic generation response and presents clear ferroelastic domains, which are rarely found in lead-free COIHSs.