Electric Field Induced Phase Transition Research Articles

Numerical simulation of electric field-induced phase transition evolution and boiling characteristics in the evaporative cooling medium C6F12O

Phase change cooling technology offers high cooling efficiency, safety, and reliability, representing a novel approach to achieving efficient heat dissipation for high-power and large-capacity electrical equipment. The formulation of the cooling medium is pivotal to phase change cooling technology. However, current media exhibit compatibility, stability, economy, and environmental friendliness deficiencies. Consideration could be given to implementing the C6F12O medium due to its superior overall performance and ability to meet the latent heat requirements in phase change cooling equipment. This paper employs a numerical simulation approach that combines the phase field method based on the Cahn-Hilliard equation with the theory of electrohydrodynamics. It investigates the impact of temperature, electric field intensity, and electric field direction on the evolution of bubble motion and the boiling state of the C6F12O medium, considering the interaction of electric-fluid-heat-phase fields. Numerical results indicate that the system undergoes initial nucleate boiling, nucleate boiling, and film boiling stages at T = 330–335 K, T = 335–350 K, and T ⩾ 355 K, respectively. The introduction of an appropriate electric field can enhance the motion evolution of C6F12O bubbles. However, attention must be paid to the formation of bubble channels under high field strength to prevent potential decreases in insulation performance. An inhomogeneous electric field in the vertical direction proves more effective in improving the bubble release rate compared to a uniform electric field. To some extent, an inhomogeneous electric field in the horizontal direction can prevent the mass accumulation of bubbles in regions of high field intensity. This research has the potential to offer theoretical guidance for the engineering application of the C6F12O phase change cooling medium.

Ultra-high strain in Bi0.5(Na0.41K0.09)TiO3 Pb-free piezoelectric ceramics modified by Sr(Hf0.5Sb0.4)O3

The lead-free piezoelectric ceramics used in piezoelectric actuators have attracted extensive attention owing to their substantial electric-field-induced strain. In this study, The (1-x)Bi0.5(Na0.41K0.09)TiO3-xSr(Hf0.5Sb0.4)O3 (BNKT-xSHS) piezoelectric ceramics were synthesized using the conventional solid-state reaction method. The impact of SHS substitution on the microstructure and electrical properties was systematically explored. Among them, the BNKT-0.015SHS sample, featuring ergodic relaxor states, demonstrates a high piezoelectric strain coefficient (d33*) of 785 p.m./V under a low electric field of 50 kV/cm(Strain = 0.392 %). It exhibits a repeatable strain value of 0.47 % under an 80 kV/cm electric field(d33* = 590 p.m./V). Moreover, the strain values remain around 0.4 % between room temperature and 100 °C, with variations within 90 %. The heightened repeatable strain response is considered to be linked to the electric field-induced reversible phase transition occurring within the ergodic relaxor state. The higher strain temperature stability is ascribed to the coexistence of quadrilateral polar nanoregions and rhombic polydomain nanoregions. This study provides an effective example for achieving significant strain responses, presenting a feasible candidate material for applications in piezoelectric actuators.

An enhanced strain response in micrometer-thick BNT-ST thin films

Lead-free Bi0.5Na0.5TiO3-SrTiO3 (BNT-ST) thin films with various thicknesses were deposited on the Pt(111)/Ti/SiO2/Si(100) substrates employing a sol-gel technique with a two-step annealing process. Despite the variations in thickness, the films exhibited a consistent polycrystalline structure, evidenced by identical diffraction peaks, albeit with differences in intensity. An imprint became evident in micro-thick films, increasing with film thickness. Also, the emergence of self-polarization was observed in thicker films detected by piezoresponse force microscopy. Noteworthy is the pronounced influence of film thickness on strain response, with the 1.38 μm-thick films demonstrating a large strain of 1.18%. The outstanding strain response can be attributed to the notable contribution of electric field-induced phase transition and polarization dynamics. This work provides a promising potential application of micrometer-thick BNT-ST thin films in advanced actuator devices.

Energy storage performance and piezoelectric response of silver niobate antiferroelectric thin film

AgNbO3-based antiferroelectric materials have attracted extensive attention in energy storage due to their double polarization-electric field hysteresis loops, but they always suffer from low breakdown strength (Eb). Films with few defects and small thickness exhibit high breakdown strength, which helps to improve energy storage performance. In the present work, an AgNbO3 film with a small thickness of ∼200 nm is prepared via pulsed laser deposition, which has a dense microstructure and a small average grain size of ∼34.5 nm. The AgNbO3 film displays an antiferroelectric nature, as confirmed by the double polarization-electric field hysteresis loops at room temperature. The room temperature phase structure of the AgNbO3 film determined by the dielectric behaviour is the antiferroelectric M2 phase. Due to the small thickness and fine grain size, a high Eb of 1200 kV/cm is obtained, which boosts a recoverable energy storage density (Wrec) of 9.3 J/cm3 and an energy efficiency (η) of 63.7 % in the AgNbO3 film. In addition, Wrec exhibits good temperature stability at 30–120 °C. The AgNbO3 film shows an obvious piezoelectric response after the electric field-induced antiferroelectric-ferroelectric phase transition as confirmed by piezoresponse force microscopy. These results provide guidance for the development of AgNbO3 antiferroelectric films and devices with good energy storage performance.

Coupled local residual shear and compressive strain in NaNbO3 ceramics under cooling

Stabilizing lead-free antiferroelectrics at room temperature is key for advancing greener and more efficient energy storage devices. While NaNbO3 solid solutions hold great promise for high energy density applications, its pure form displays structural instabilities arising from irreversible electric-field induced phase transitions and/or an undesired coexistence with its ferroelectric polymorph. To unravel how mechanical constraints imposed by residual stresses, structural defects, and microstructure disrupt the stability of the NaNbO3 antiferroelectric state, we used in situ Dark-Field X-ray Microscopy to map local microstructural deformations in a single embedded {100}pc grain. By replicating typical heat treatment conditions, we show that the ferroelectric phase nucleates as a result of the coupled interplay between residual shear and compressive strain distributions that manifest during cooling towards ambient temperature. In addition, the microstrain relaxation behavior indicates that long-range defects preferentially nucleate at the expense of the antiferroelectric phase in regions at sub-micrometer distances from the grain center. Our findings illustrate that adequate temperature control during low temperature sintering, heat treatments, or in operando conditions may be vital in dictating the structure-property relationships of NaNbO3 ceramics, ensuring their suitability for efficient energy storage applications.

Stress and electric field induced phase transitions for ultra high energy conversion in ferroelectrics

This work focuses on energy harvesting of ferroelectric relaxors PMN-25PT and PZN-8PT single crystals with high uniaxial stress and electric field. Ericsson cycle, which consists of applying and releasing electric field and stress at different steps of the cycle, has been used. A large energy density for PZN-8PT high as 410 mJ/cm3 was obtained. Different working temperatures were tested by experiment and modeled via Landau–Devonshire theory. Optimal working temperatures were identified for high level energy conversion and were successfully predicted by simulation. It appeared that the optimum working temperature was different from that optimizing the d33. Polarization mechanisms induced by these extreme conditions for energy harvesting are explained in the frame of experimental and modeling results. The results obtained at high stress levels tend to indicate that operating along the polarization direction yields the best results, which contradicts conclusions drawn in the case of domain engineered crystals.

Electrocaloric effect in pure and NaNbO3-modified Na0.5Bi0.5TiO3–BaTiO3 solid solutions near the morphotropic phase boundary

Morphotropic phase boundary of ferroelectric solid solutions attracts interest with respect to not only improved piezoelectric properties but also the electrocaloric effect, which is attractive to build new-generation cooling devices. In the present study, the electrocaloric effect in (1 − x − y)Na0.5Bi0.5TiO3–xBaTiO3–yNaNbO3 near its morphotropic phase boundary is studied by direct measurements of temperature change ΔT. ΔT maximum is observed in the region of depolarization temperature, where the major contribution comes from an entropy jump at the electric field-induced phase transition. Differences between ΔT values measured when an electric field pulse is applied and removed are explained by slow domain rearrangement in the ferroelectric phase and metastability of phases close to the depolarization temperature. Among studied compositions, the highest value of ΔT is obtained for the compositions 0.94Na0.5Bi0.5TiO3–0.06BaTiO3 and 0.93Na0.5Bi0.5TiO3–0.06BaTiO3–0.01NaNbO3 in the region of depolarization temperature. Examples of the comparison of the directly measured values of ΔT and the values calculated using the Maxwell relation revealing inconsistency between the two methods in the ferroelectric and the nonferroelectric phase are presented.

Giant strain performance of lead-free relaxor piezoceramics through synergistic compositional and defect engineering

For applications involving high-precision displacement actuators, piezoceramics exhibiting extensive strain and minimal hysteresis are much sought-after. However, achieving extensive strain concurrent with low hysteresis remains a formidable challenge. We hereby propose an innovative design approach, synergistically harnessing compositional and defect engineering, to concurrently boost the strain response and mitigate hysteresis in (Na0.5Bi0.5)TiO3 (NBT)-based ceramics. The defect dipoles are elaborately designed and introduced into the mixed rhombohedral (R) and tetragonal (T) phases system, which causing reversible domain switching, heightening recoverability of electric-field-induced phase transition and augmenting the electrostrictive effect. The synergy of defect dipoles leading to reversible domain switching and electric field-induced phase transitions is further validated via phase-field simulations. Ultimately, a giant strain of 0.62% with low hysteresis of 10.9% and correspondingly high d33* of 1033 pm V−1 were concurrently realized in the designed NBST(1-x)Mnx (x = 0.3%) specimen. This study opens up a feasible and effective way to design piezoelectric materials with both a giant strain and a narrow hysteresis in lead-free actuator materials.

MnO2 doping stabilized antiferroelectric P phase and underlying physical mechanism in NaNbO3-SrTiO3 lead-free ceramics

The incorporation of a few amount of MnO2 into 0.88NaNbO3-0.12SrTiO3 lead-free ceramics was found to effectively stabilize the antiferroelectric orthorhombic P phase before its transition into antiferroelectric orthorhombic R phase, consequently featuring completely reversible electric field-induced antiferroelectric-ferroelectric phase transition. Not only reproducible double polarization hysteresis loops but also repeated sprout-like strain-field curves ensure great application potentials in large-displacement lead-free actuators owing to both large repeatedly-utilized strains of ∼0.33% and low driving field of ∼11 kV/mm. Combined results of XPS, Raman spectroscopy and dielectric properties indicate that the stabilized antiferroelectric P phase was closely related to the reduced B-site cation polarizability and oxygen vacancy concentration, while a slight change in antiferrodistortive degree would discourage the P-R phase transition. These results indicate that ionic doping is an alternative method to alter the antiferroelectric P phase stability of NaNbO3-based lead-free ceramics by synergistically considering the influencing factors of phase and crystal structure stability.

Design and development of a new lead-free BiFeO3-BaTiO3 quenched ceramics for high piezoelectric strain performance

Designing a new high-performance lead-free ceramic has become a cutting-edge research topic due to growing concerns about the toxic nature of lead-based materials. In this work, a convenient strategy of compositional design and domain engineering is applied to the lead-fee BiFeO3-BaTiO3 ceramics which provides a flexible polarization free-energy profile for domain switching. Here, simultaneously enhanced dynamic piezoelectric constant (d33* ≈ 772 pm/V) and a good thermal-stability (Δd33* ≈ 26% over the temperature of 20–180 °C) are achieved with a high Curie temperature (TC) of 432 °C. This high piezoelectric strain performance is collectively attributed to multiple effects such as thermal quenching, suppression of defect charges by donor doping, chemically induced local structure heterogeneity, and electric field-induced phase transition. Furthermore, the addition of BT content decreased octahedral tilting that reduce anisotropy for domain switching and increased in tetragonality (cT/aT) providing a wider polar length for B-site cation displacement, leading to high piezoelectric strain performance. Atomic-resolution transmission electron microscopy and piezoelectric force microscopy combined with X-ray diffraction results strongly support the origin of high piezoelectricity. The high and temperature-stable piezoelectric strain response of this work is superior to those of other lead-free ceramics. The synergistic approach of composition design and the concept present here for the origin of high strain response provides a paradigm for the development of new materials for high-temperature piezoelectric actuator applications.

Electric field induced phase transition in multicomponent ceramics based on PbMg1/3Nb2/3O3–PbTiO3

Multicomponent ceramics based on PbMg1/3Nb2/3O3–PbTiO3 system were studied using X-ray diffraction at high electric fields. It was shown that electric field induced phase transition from initial pseudocubic phase to tetragonal one occurs at E > 5 kV/cm. Analysis of the intensities of the 200 X-ray peak components reveals the parameters of the tetragonal unit cell (с = 4.036 Å and а = 4.021 Å) and the degree of preferential domain orientation (≈ 35%) at E = 12 kV/cm. The results of X-ray diffraction studies are in a good agreement with the field-induced behavior of the macroscopic responses: strain, polarization, and dielectric permittivity.

Discovery of Nanoscale Electric Field‐Induced Phase Transitions in ZrO2

AbstractThe emergence of ferroelectric and antiferroelectric properties in the semiconductor industry's most prominent high‐k dielectrics, HfO2 and ZrO2, is leading to technology developments unanticipated a decade ago. Yet the failure to clearly distinguish ferroelectric from antiferroelectric behavior is impeding progress. Band‐excitation piezoresponse force microscopy and molecular dynamics are used to elucidate the nanoscale electric field‐induced phase transitions present in ZrO2‐based antiferroelectrics. Antiferroelectric ZrO2 is clearly distinguished from a closely resembling pinched La‐doped HfO2 ferroelectric. Crystalline grains in the range of 3 – 20 nm are imaged independently undergoing reversible electric field induced phase transitions. The electrically accessible nanoscale phase transitions discovered in this study open up an unprecedented paradigm for the development of new nanoelectronic devices.

Tunable polarization-drived superior energy storage performance in PbZrO 3 thin films

Antiferroelectric PbZrO₃ films have great potential to be used as the energy storage dielectrics due to the unique electric field-induced phase transition character. But the phase transition process always accompanies polarization hysteresis effect that induces large energy loss and lowers the breakdown strength, leading to inferior energy storage density as well as low efficiency. In this work, the synergistical strategies by doping smaller ions of Li⁺-Al³⁺ to substitute Pb²⁺ and lowering the annealing temperature from 700℃ to 550℃ are proposed to change the microstructure and tune the polarization character of PbZrO₃ films, excepting to dramatically improve the energy storage performances. The prepared Pb_(1-x)(Li_0.5Al_0.5)_xZrO₃(abbreviated as P_(1-x)(L_0.5A_0.5)_xZO) films exhibit ferroelectric-like (<em>FE</em>) rather than antiferroelectric (<em>AFE</em>) character once the doping content of Li⁺-Al³⁺ ions reaches 6 mol%, accompanying a significant improvement of energy storage density of 49.09 J/cm³,but energy storage efficiency is only 47.94% due to the long-correlation of ferroelectric domains. Accordingly, the low-temperature annealing is carried out to reduce the crystalline degree and the polarization loss. P_0.94(L_0.5A_0.5)_0.06ZO films annealed at 550℃ deliver a linear-like polarization rather than ferroelectric-like behavior annealed at 700℃, the lowered remanent polarization as well as improved breakdown strength (4814 kV/cm) result in the superior energy storage density of 58.7 J/cm³ and efficiency of 79.16%, simultaneously possessing excellent frequency and temperature stability, and good electric fatigue tolerance.

Nanoscale investigation on electric field induced ferroelectric phase transitions in the rhombohedral PMN-PT single crystal

The excellent piezoelectric property of Pb(Mg1/3Nb2/3)O3-PbTiO3(PMN-PT) single crystals has attracted increasing attentions for their application in electromechanical devices. Generally, the electric field induced phase transition is an important contribution to the piezoelectric response. Understanding the pathway of electric field induced phase transition is essential for the practical application of PMN-PT crystals. Here, evolution of the domain structure and surface screening charges during phase transitions in the (001) oriented 0.72PMN-0.28PT crystal were studied at nanoscale via piezo-response force microscopy (PFM) and Kelvin probe force microscopy (KPFM). In combination with confocal polarized Raman spectroscopy, electric field induced phase transitions were locally studied. PFM tip bias poling in 0.72PMN-0.28PT single crystal results in a rhombohedral to monoclinic phase transition. And the monoclinic phase relaxes back to the rhombohedral at elevated temperatures. Our work provides nanoscale investigations on the electric field induced phase transition, and will be instructive for the practical application of PMN-PT single crystals.

Alkali-earth metal ion inducing multiphase transition of lanthanum-free Pb(Zr0.5Sn0.5)O3 ceramics improves the energy storage properties

Constructing the stepwise phase transition can delay the polarization process of antiferroelectric ceramics, possessing certain significance for improving the energy storage density. However, the common multiphase transitions are obtained in the rare-earth ions doped PbZrO3-based systems. In the present work, the multiphase transition can also be induced in the lanthanum-free Pb(Zr0.5Sn0.5)O3 matrix with mere doping of the alkali-earth metal ion Sr. The introduction of Sr endows the matrix with a higher lattice distortion and the reduced phase-transition temperature. Moreover, related to the induced stepwise electric field-induced phase transition, the energy storage properties are remarkably enhanced to 10.5 J/cm3 and 83.2% when the substitution content of Sr is 3 mol. %. Sr modification can adjust the phase structure by regulating the phase stability of the matrix and suppress the leakage current originating from the structural changes. This work provides a successful attempt that the phase structure and energy storage performance of antiferroelectric ceramics can also be effectively controlled through cheaper and simpler element modification. The optimized energy storage performance provides a new material selection for pulsed power devices.

Correlation between multi-factor phase diagrams and complex electrocaloric behaviors in PNZST antiferroelectric ceramic system

Ferroelectric (FE) phase transition with a large polarization change benefits to generate large electrocaloric (EC) effect for solid-sate and zero-carbon cooling application. However, most EC studies only focus on the single-physical factor associated phase transition. Herein, we initiated a comprehensive discussion on phase transition in Pb_0.99Nb_0.02[(Zr_0.6Sn_0.4)_1−<i>x</i>Ti_<i>x</i>]_0.98O₃ (PNZST100<i>x</i>) antiferroelectric (AFE) ceramic system under the joint action of multi-physical factors, including composition, temperature, and electric field. Due to low energy barrier and enhanced zero-field entropy, the multi-phase coexistence point (<i>x</i> = 0.12) in the composition–temperature phase diagram yields a large positive EC peak of maximum temperature change (Δ<i>T</i>_max) = 2.44 K (at 40 kV/cm). Moreover, the electric field–temperature phase diagrams for four representative ceramics provide a more explicit guidance for EC evolution behavior. Besides the positive EC peaks near various phase transition temperatures, giant positive EC effects are also brought out by the electric field-induced phase transition from tetragonal AFE (AFE_T) to low-temperature rhombohedral FE (FE_R), which is reflected by a positive-slope boundary in the electric field–temperature phase diagram, while significant negative EC responses are generated by the phase transition from AFE_T to high-temperature multi-cell cubic paraelectric (PE_MCC) with a negative-slope phase boundary. This work emphasizes the importance of phase diagram covering multi-physical factors for high-performance EC material design.

Achieving Ultrahigh Energy Storage Density of La and Ta Codoped AgNbO3 Ceramics by Optimizing the Field-Induced Phase Transitions

Energy storage capacitors are extensively used in pulsed power devices because of fast charge/discharge rates and high power density. However, the low energy storage density and efficiency of dielectric capacitors limit their further commercialization in modern energy storage applications. Lead-free AgNbO3-based antiferroelectric (AFE) ceramics are considered to be one of the most promising environmentally friendly materials for dielectric capacitors because of their characteristic double polarization-electric field hysteresis loops with small remanent polarization and large maximum polarization. An enhancement of these characteristics allows achieving a synergistic improvement of both the energy storage density and efficiency of the antiferroelectric materials. This work reports on a feasible codoping strategy enabling the preparation of AgNbO3-based ceramics with high energy storage performance. An introduction of La3+ and Ta5+ ions into the AgNbO3 perovskite lattice was found to increase the structural stability of the antiferroelectric phase at the expense of a reduction of local polar regions, resulting in the shifting of the electric field-induced antiferroelectric-ferroelectric phase transition toward higher fields. An ultrahigh recoverable energy storage density of 6.73 J/cm3 and high energy storage efficiency of 74.1% are obtained for the Ag0.94La0.02Nb0.8Ta0.2O3 ceramic subjected to a unipolar electric field of 540 kV/cm. These values represent the best energy performance in reported lead-free ceramics so far. Hence, the La3+/Ta5+ codoping has been shown to be a good route to improve the energy storage properties of AgNbO3 ceramics.

Phase transition-induced initial decomposition of nitrogen-rich binary CN compound 2,2'-azobis(5-azidotetrazole) and its precursor 2-amino-5-azidotetrazole via tetrazole ring opening under external electric fields: a comparative DFT-D study.

A comparative DFT-D study was performed to investigate the external electric field-induced crystal structures, electronic features, Hirshfeld surfaces, vibrational properties and initial decomposition mechanisms of nitrogen-rich binary CN compound 2,2'-azobis(5-azidotetrazole) (C2N16) and its precursor 2-amino-5-azidotetrazole (CH2N8). The results show that there exist phase transitions at the critical points of 0.006 a.u. and 0.008 a.u. for CH2N8 and C2N16, respectively, which are embodied in various properties of these compounds and induce their initial decomposition of the tetrazole ring opening via the breaking of N-N single bonds. The analysis of band gaps and density of states suggests the external electric field-induced enhancing ability for electron transition from the occupied orbitals to empty ones and N-N bond breaking may be the initial decomposition pathway for them. The variations in Hirshfeld surfaces indicate the spatial change and adjustment of non-bonding interactions in the two crystals. The discussions on vibrational properties indicate that IR characteristic peaks of all vibrational modes in the two crystals show a gradual red shift toward a low frequency region. The external electric field-induced initial decomposition pathways of both crystals are tetrazole ring opening via the breaking of a N-N single bond. Our findings provide insights for a comprehensive understanding of external electric field-induced phase transition and initial decomposition mechanisms of nitrogen-rich binary CN energetic compounds.

Dielectric and piezoelectric properties of 0.8Na0.5Bi0.5TiO3-0.2BaTiO3 modified with sodium niobate

In this paper, we present the dielectric and piezoelectric properties of tetragonal 0.8Na0.5Bi0.5TiO3-0.2BaTiO3 modified with NaNbO3 ((1-x)[0.8Na0.5Bi0.5TiO3-0.2BaTiO3]-xNaNbO3). Our experimental study has revealed that the ferroelectric phase in these compositions is suppressed with the increase of sodium niobate concentration. A broad anomaly, resembling relaxor ferroelectrics, appears in the 325–450 K temperature interval. The investigation of the electric field dependence of polarization has indicated that the double hysteresis loop behaviour is characteristic of the modified compositions, which is associated with the 1st order phase transition under the applied electric field. The experiments below room temperature have revealed that the range of stability of the ferroelectric phase is shifted to lower temperatures upon the increase of sodium niobate concentration. The electromechanical displacement in the modified compositions shows a similar maximum displacement in the whole concentration range. The electromechanical response in 0.8Na0.5Bi0.5TiO3-0.2BaTiO3 solid solutions is due to the piezoelectric effect, while, in the mixed compositions, it is related to the jump-like change of the lattice constants in the vicinity of electric fieldinduced 1st order phase transition.

Сorrelation between structural phase coexistence and magnetic response of Eu-doped BiFeO3 at the morphotropic phase boundary

Bi1-xEuxFeO3 ceramic samples with x = 0.1–0.2 have been synthesized to investigate the correlation between the multiphase coexistence and magnetic response. X-ray diffraction and Raman scattering spectra reveal the structural transition from the R3c rhombohedral to Pnma nonpolar orthorhombic structures via partial formation of Pbam antipolar orthorhombic structure with increasing of Eu concentration, thus disclosing the mixed phase state in the composition range of 0.10 ≤ x ≤ 0.18. The magnetic measurement at a high magnetic field reveals a weak ferromagnetic behavior; the magnetization reaches maximum value in phase mixture compounds and then decreases in a single phase compound. The different magnetic response under high and low applied fields is explained in terms of the phase boundary (PB) spins and the intrinsic antiferromagnetic spins. The characteristic of the PB spins contributing to the magnetic properties have been determined by the study on the magnetic aging effect, electric field-induced phase transition, and field step-dependent hysteresis loops.