Search

The origin of the strong piezoelectric phenomenon in PbZr1−xTixO3 (PZT) perovskites still suffers from a lack of complete understanding. It concerns the distinction between the intrinsic and extrinsic mechanisms that govern PZT's piezo activity. These two mechanisms have been investigated in single crystal PbZr0.54Ti0.46O3 at the morphotropic phase boundary. After poling in a DC electric field, the piezoelectric properties were examined on the same crystal by observing piezoelectric resonances to determine the piezoelectric coefficient d31 and measuring quasistatic deformation to determine the coefficient d33. The domain populations were investigated during and after poling in a DC electric field. These populations were also investigated as a function of DC fields for strengths similar to those used to measure quasistatic piezoelectric properties for a poled crystal. The experiments indicate that the intrinsic origin of the enhancement of the piezoelectric properties is connected with a change in the population of domains with monoclinic symmetry, in which there is an easy polarization rotation under the action of the electric field.

Struvite (MgNH4PO4·6H2O) is a mineral first identified in 1845. It is tested for several reasons: (1) it is a problem in liquid wastewater treatment plants; (2) on the other hand, it is recovered from this wastewater because of phosphorus, magnesium, and nitrogen; (3) it is the main component of infectious urinary stones. In this paper, we present the first experimental evidences of the ferroelectric nature of struvite at room temperature. Struvite shows a hysteresis loop and spontaneous electric polarization that can be reversed by an application of an external electric field. The measured value of residual polarization of struvite is equal to 0.95 μC/cm2. We also report observations of the ferroelectric domains in struvite using birefringence imaging technique. The non-centrosymmetry of the crystal lattice is confirmed with the use of the Kurtz−Perry powder test. The second harmonic generation response for struvite in relation to that of potassium dihydrogen phosphate is 0.36. We suggest that ferroelectric properties for struvite, in particular, spontaneous polarization, can have a significant impact on the behavior of struvite in aqueous solutions, such as liquid wastewater or urine.

Controversy in the description/identification of so-called intermediate phase(s) in PbHfO3, stable in the range ∼420–480 K, has existed for a few decades. A synchrotron diffraction experiment on a partially detwinned crystal allowed the structure to be solved in the superspace groupImma(00γ)s00 (No. 74.2). In contrast to some previously published reports, in the pure compound only one distinct phase was observed betweenPbamPbZrO3-like antiferroelectric andPm3mparaelectric phases. The modulation vector depends only slightly on temperature. The major structure modulation is associated with the displacement of lead ions, which is accompanied by a smaller amplitude modulation for the surrounding O atoms and tilting of HfO6octahedra. Tilting of the octahedra results in a doubling of the unit cell compared with the parent structure.

In the archetypal antiferroelectric PbZrO3, antiparallel electric dipoles cancel each other, resulting in zero spontaneous polarisation at the macroscopic level. Yet in actual hysteresis loops, the cancellation is rarely perfect and some remnant polarization is often observed, suggesting the metastability of polar phases in this material. In this work, using aberration-corrected scanning transmission electron microscopy methods on a PbZrO3 single crystal, we uncover the coexistence of the common antiferroelectric phase and a ferrielectric phase featuring an electric dipole pattern of "up down up". This dipole arrangement, predicted by Aramberri et al. (2021) to be the ground state of PbZrO3 at 0K, appears at room temperature in the form of translational boundaries that aggregate to form wider stripe domains of the polar phase embedded within the antiferroelectric matrix.

In this paper, we present the first experimental evidence of the piezoelectric nature of struvite (MgNH4PO4·6H2O). Using a single diffusion gel growth technique, we have grown struvite crystals in the form of plane parallel plates. For struvite crystals of this shape, we measured the piezoelectric coefficients d33 and d32. We have found that at room temperature the value of piezoelectric coefficient d33 is 3.5 pm/V, while that of d32 is 4.7 pm/V. These values are comparable with the values for other minerals. Struvite shows stable piezoelectric properties up to the temperature slightly above 350 K, for the heating rate of 0.4 K/min. For this heating rate, and above this temperature, the thermal decomposition of struvite begins, which, consequently, leads to its transformation into dittmarite with the same non-centrosymmetric symmetry as in case of struvite. The struvite-dittmarite transformation temperature is dependent on the heating rate. The higher the heating rate, the higher the temperature of this transformation. We have also shown that dittmarite, like struvite exhibits piezoelectric properties.

The effect of hydrostatic pressure on phase transitions in lead hafnate (PbHfO3) has been studied by the methods of X-ray diffraction and X-ray diffuse scattering. The measurements were performed in the temperature range of 182 < T < 316°C and the pressure range of 1.6 < P < 2.6 GPa. Four regions characterized by different X-ray diffraction patterns and corresponding to an antiferroelectric phase, phases with a long-wavelength modulation of the lead sublattice, and phases with different distortions of the oxygen sublattice are identified. In the temperature region immediately above the region of phases with a long-wavelength modulation, a temperature-dependent maximum in the distribution of diffuse scattering was detected, which means that such a modulation is formed due to condensation of an incommensurate soft mode.

The effects of rhodium (Rh) doping on the elastic properties and phase transition behaviors of reduced BaTiO3 single crystals were investigated in the paraelectric phase by using Brillouin spectroscopy. The Rh doping induced changes in the elastic stiffness coefficients and the elastic anisotropy parameter. The degree of softening of (C11 − C12)/2 became more substantial with Rh doping, indicating that the polarization fluctuations were enhanced by heterovalent Rh3+ doping. This was supported by the much larger temperature range over which the nonzero birefringence was observed. Free charge carriers introduced by Rh doping and oxygen vacancies in the reduced BaTiO3 and their interactions with the lattice seem to be the origin of these anomalous changes in the elastic properties.

Elastic anisotropy and slowness curves of barium titanate (BaTiO3) single crystal in the paraelectric phase were investigated by using Brillouin spectroscopy. The directional dependence of sound velocities of the longitudinal and the transverse acoustic waves in the (001) plane showed a four-fold symmetry typical in the cubic phase. Especially, one of the two transverse modes exhibited a substantial softening along the directions. The sound velocity of this mode decreased significantly as temperature decreased toward the transition temperature, which corresponded to the elastic stiffness coefficient (C11 – C12)/2. This result suggests the tetragonal instability caused by the precursor polar clusters in the paraelectric phase of BaTiO3.

Lead zirconate-titanate PbZr0.70Ti0.30O3 ceramics doped with bismuth oxide has been investigated. Dielectric and optical measurements were performed to check the dopant influence on phase transitions and pre-transitional effects. It has been postulated that the temperature at which maximum permittivity occurs is not connected with structural phase transitions.

For the first time, a weak ferromagnetic hysteresis loop at room temperature has been observed in PbZr1−xTixO3 (PZT) single crystals. The occurrence of these properties has been related to the presence of oxygen vacancies and/or lower oxidation state of titanium. This proves that ferroelectric and ferromagnetic properties can occur simultaneously in this “famous” piezoelectric perovskite without any magnetic dopant.

The large electrocaloric coupling in PbZrO3 allows using high-speed infrared imaging for visualizing anti-ferroelectric switching dynamics via the associated temperature change. It is found that in ceramic samples of homogeneous temperature and thickness, switching is fast due to the generation of multiple nucleation sites, with devices responding in the millisecond range. By introducing gradients of thickness, however, it is possible to change the dynamics to propagation limited, whereby a single-phase boundary sweeps across the sample like a cold front, at a speed of ≈20 cm s−1. Additionally, introducing thermostatic temperature differences between two sides of the sample enables the simultaneous generation of a negative electrocaloric effect on one side and a positive one on the other, yielding a Janus-like electrocaloric response., With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (SEV-2017-0706)

An expansive library of structurally complex two-dimensional (2D) and three-dimensional (3D) lead halide perov-skites has emerged over the past decade, finding applications in various aspects of photon management: photovoltaics, photo-detection, light emission, and nonlinear optics. Needless to say, the highest degree of structural plasticity enjoys the former group, offering a rich playground for modifications of relevant optoelec-tronic parameters such as exciton energy. Structural tailorability is reflected in the ease of modification of the chemistry of the organic layers residing between inorganic slabs. In this vein, we show that the introduction of methylhydrazinium cation (MHy+, CH3NH2NH2+) into 2D perovskite gives a material with a record low separation of the inorganic layers (8.91 Å at 300 K). Optical studies showed that MHy2PbBr4 features the most red-shifted excitonic absorption among all known A2PbBr4 compounds as well as a small exciton binding energy of 99.9 meV. MHy2PbBr4 crystallizes in polar Pmn21 symmetry at room emperature (phase III) and at 351 K undergoes a phase transition to modulated Pmnm phase (II) followed by another phase transition at 371 K to Pmnm phase (I). The ferroelectric property of room-temperature phase III is inferred from switching of the pyrocurrent, dielectric measurements, and optical birefringence results. MHy2PbBr4 exhibits multiple nonlinear optical phenomena such as second-harmonic generation, third-harmonic generation, two-photon excited luminescence, and multiphoton excited luminescence. Analysis of MHy2PbBr4 single-crystal luminescence spectra obtained through linear and nonlinear optical excitation pathways indicates that free exciton emission is readily probed by the ultraviolet excitation, whereas crumpled exciton emission is detected under two- and multiphoton excitation conditions. Overall, our results demonstrate that incorporation of MHy+ into the organic layer is an emergent strategy for obtaining a 2D perovskite with polar character and multifunctional properties.

We have studied the electrocaloric response of the archetypal antiferroelectric PbZrO3 as a function of voltage and temperature in the vicinity of its antiferroelectric-paraelectric phase transition. Large electrocaloric effects of opposite signs, ranging from an electrocooling of −3.5 K to an electroheating of +5.5K, were directly measured with an infrared camera. We show by calorimetric and electromechanical measurements that the large negative electrocaloric effect comes from an endothermic antiferroelectric-ferroelectric switching, in contrast to dipole destabilization of the antiparallel lattice, previously proposed as an explanation for the negative electrocaloric effect of antiferroelectrics., We acknowledge financial support to ICN2, which is funded by the CERCA programme/Generalitat de Catalunya and by the Severo Ochoa programme of the Spanish Ministry of Economy, Industry and Competitiveness (MINECO, Grant No. SEV-2017-0706). We also acknowledge support to Plan Nacional (MINECO Grant No. MAT2016-77100-C2-1-P) and MINECO Grant No. BES-2016-077392. R.F., Y.N., and E.D acknowledge the Luxembourg National Research Fund (FNR) for funding part of this research through the Projects No. CAMELHEAT/C17/MS/11703691/Defay and No. COFERMAT/P12/4853155/Kreisel. This work was also supported in part by the Spanish Ministry of Science, Innovation and Universities under the HIPERCELLS Project No. RTI2018-098392-B-I00, the Regional Government of the Generalitat de Catalunya under Grants No. 2017 SGR 1384 and No. 217 SGR 1384, the Consejo Superior de Investigaciones Científicas through internal research programs with Identification No. 201850I063 and No. 201950E036. This work was also supported by the National Science Centre, Poland, within the Project No. 2016/21/B/ST3/02242.

Phase transition is established to govern electrostatic energy storage for antiferroelectric (AFE)‐type dielectric capacitors. However, the source of inducing the phase transition and the pathway of storing the energy remains elusive so far given the ultrafast charging/discharging process under normal working conditions. Here, by slowing down the phase‐transition speed using electron‐beam irradiation as an external stimulus, the in situ dynamic energy‐storage process in AFE PbZrO3 is captured by using atomic‐resolution transmission electron microscopy. Specifically, it is found that oxygen‐lead‐vacancy‐induced defect core acts as a seed to initiate the antiferrodistortive‐to‐ferrodistortive transition in antiparallel‐Pb‐based structural frames. Associated with polarity evolution of the compressively strained defect core, the ferroelectric (FE)–ferrodistortive state expands bilaterally along the b‐axis direction and then develops into charged domain configurations during the energy‐storage process, which is further evidenced by observations at the ordinary FE states. With filling the gap of perception, the findings here provide a straightforward approach of unveiling the unit‐cell‐wise energy storage pathway in chemical defect‐engineered dielectric ceramics.

The Mössbauer effect was used to study the structural transitions in a PbZr

Antiferroelectric‐based dielectric capacitors are receiving tremendous attention for their outstanding energy‐storage performance and extraordinary flexibility in collecting pulsed powers. Nevertheless, the in situ atomic‐scale structural‐evolution pathway, inherently coupling to the energy storage process, has not been elucidated for the ultimate mechanistic understanding so far. Here, time‐ and atomic‐resolution structural phase evolution in antiferroelectric PbZrO3 during storage of energy from the electron‐beam illumination is reported. By employing state‐of‐the‐art negative‐spherical‐aberration imaging technique, the quantitative transmission electron microscopy study presented herein clarifies that the hierarchical evolution of polar oxygen octahedra associated with the unit‐cell volume change and polarization rotation accounts for the stepwise antiferroelectric‐to‐ferroelectric phase transition. In particular, an unconventional ferroelectric category—the ferrodistortive phase characteristic of a unique cycloidal polarization order—is established during the dynamic structure investigation. Through clarifying the atomic‐scale phase transformation pathway, findings of this work unveil a new territory to explore novel ferrodistortive phases in energy‐storage materials with the nonpolar‐to‐polar phase transitions.

Lead hafnate single crystals were characterized using single crystal x-ray diffraction under simultaneous application of hydrostatic pressure and high temperatures. The information on the structure of two intermediate phases, situated between antiferroelectric and paraelectric phases in the pressure-temperature phase diagram, has been obtained. The lower-temperature intermediate phase is characterized by incommensurate displacive modulations in Pb sublattice. The higher-temperature intermediate phase is characterized by oxygen framework distortion, primarily in the form of anti-phase tilts of the oxygen octahedra, which is also present in the lower-temperature intermediate phase.

Lemon-yellow single crystals of Eu2[SiO4] were obtained by reaction of elemental europium with Eu2O3 in the presence of SiO2 carried out in evacuated silica ampules at 1373 K for 48 h followed by constant cooling to room temperature with 120 K per hour. Eu2[SiO4] crystallizes at room temperature in the larnite-type structure of β-Ca2[SiO4] (monoclinic, P21/n) with parameters a = 565.02(5), b = 709.15(6), c = 975.84(8) pm, β = 92.614(3)° for Z = 4. At 452 K it undergoes a reversible phase transition to an incommensurate structure similar to the isotypic compounds Sr2[SiO4] and K2[SeO4]. The phase transition energy was determined to 0.54(2) J·g–1 by DSC measurements and temperature dependent birefringence measurements show that the phase transition exhibits a significant hysteresis. Refinements of the structure of Eu2[SiO4] based on single crystal X-ray diffraction data show that the high temperature modification crystallizes in the orthorhombic space group Pnma(α00)0ss with a = 710.16(6), b = 566.93(5), c ...

Antiferroelectric-based dielectric capacitors are receiving tremendous attention for their outstanding energy-storage performance and extraordinary flexibility in collecting pulsed powers. Nevertheless, the in situ atomic-scale structural-evolution pathway, inherently coupling to the energy storage process, has not been elucidated for the ultimate mechanistic understanding so far. Here, time- and atomic-resolution structural phase evolution in antiferroelectric PbZrO

We have investigated in detail the lattice dynamics of five different perovskite titanates ATiO3 (A = Ca, Sr, Ba, Pb, Eu) where the A sites are occupied by +2 ions. In spite of the largely ionic character of these ions, the properties of these compounds differ substantially. They range from order/disorder like, to displacive ferroelectric, quantum paraelectric, and antiferromagnetic. All compounds crystallize in the cubic structure at high temperature and undergo structural phase transitions to tetragonal symmetry, partly followed by further transitions to lower symmetries. Since the TiO6 moiety is the essential electronic and structural unit, the question arises, what makes the significant difference between them. It is shown that the lattice dynamics of these compounds are very different, and that mode-mode coupling effects give rise to many distinct properties. In addition, the oxygen ion nonlinear polarizability plays a key role since it dominates the anharmonicity of these perovskites and determines the structural instability.

Influence of heterovalent Nb5+ doping of antiferroelectric PbZrO3 single crystal has been investigated. This kind of doping, producing defects in the perovskite matrix, influences the lattice instabilities responsible for phase transition at TC, and for inducing pre- and post-transitional effects. The dielectric, electromechanical, and optical properties were investigated. Opposite to their ceramic analogues, the investigated single crystals show a new phase transition and enlarged temperature ranges of lattice instabilities.

Perovskite oxides ABO3 offer a vast playground for applications and basic research. Especially multifunctionality is a frequently targeted aim, since the replacement of the A and/or B sublattice ions easily changes the properties of the system. Here we concentrate on the perovskite EuTiO3 (ETO) which was ignored by the scientific community for a long time. We review recent results on it and show that this compound provides many surprises which may offer novel device techniques and applications. In particular we demonstrate that far above its Neel temperature TN = 5.7 K magnetism exists and new magneto-dielectric-elastic coupling is at work. From capacitance and muon spin rotation (μSR) data we conclude that the phase diagram of ETO is much more complex than believed and a variety of new phases are described.

Professor Wojciech Kuczynski, a Research Staff Member at the Institute of Molecular Physics of the Polish Academy of Sciences in Poznan, Poland, passed away on 5 December 2020.Professor Kuczynski w...

PbZr1-xTixO3 perovskite materials, known as PZT, are highly applicable, mainly due to their extraordinary piezoelectric properties. Recently, a technology of PZT crystals growth has been elaborated and opened new investigation possibilities for these compounds. In this paper, we demonstrate a highly piezoelectric response in PbZr0.87Ti0.13O3 single crystal. Under the action of an electric field, the piezoelectric coefficient d33 turns out to be over 2500 pm V-1. The optical studies performed have proved a significant influence of the domain dynamics on such high-efficiency piezoelectric response. Monoclinic M and rhombohedral R phases have been observed in the lead zirconate-titanate crystals with a low Ti content. This coexistence of phases with different symmetries and dense domain walls are the primary sources of high piezoelectric response. We have observed that strong electric fields may act on randomly oriented polarization vectors so that the total piezoelectric activity disappears, and the unusual isotropization point near 250 °C appears.

In many cases, functionality is connected with the response of a material to the action of an external electric field. In oxidic perovskites, so widely used in practice, a disadvantage is their surface chemical instability when subjected to an electric field. That is why investigations of the influence of a high intensity alternating electric field on the phase transition temperatures and chemical properties of the surface and bulk of single crystals of PbZrO3 intentionally made defective by doping with niobium have been undertaken. It has been demonstrated that defects produced through the electro-degradation process make the low-field dielectric response a highly diffusive one, but they do not obscure the sharp phase transitions detected by temperature changes in the bulk piezoelectric and electrostrictive deformation around the critical temperature. Based on XPS spectra, the types of defects at the surface and in the bulk of as-grown single crystals caused by the electric field action are identified. It has been shown that the surface–bulk interrelation in ferroic lead zirconate and solid solutions based on this material has to be taken into account while trying to use them as high quality functional materials.

We report the high-temperature and high-pressure single-crystal x-ray diffraction study of PbHfO3. The increase of pressure enables an additional intermediate phase, located between the cubic and incommensurate phases, and characterized by superstructure reflections indicating the presence of anti-phase oxygen octahedral tilts. The temperature-dependent diffuse peak at an incommensurate position is much better pronounced at higher pressures (~ 2 GPa) than at lower pressures (~ 1.1 GPa), which we interpret as enhancing of the incommensurate soft mode on pressure increase. Several peculiarities in the behavior of superstructural reflections at M- and X- points are reported and discussed.

We report a type of structural phase transitions in dielectric materials: the triggered incommensurate (IC) transition. We demonstrate evidence for such a transition in the perovskite antiferroelectric ${\mathrm{PbHfO}}_{3}$ by means of single-crystal x-ray diffraction, diffuse, and inelastic-scattering experiments, which we interpret using the Landau theory of phase transitions. This transition is not driven by an IC soft mode, as is the case for the majority of IC dielectrics, but by the soft mode associated with a different, coexisting order parameter related to antiferrodistortive (AFD) tilts of the oxygen octahedra. When cooling from the high-temperature cubic phase these two order parameters are established simultaneously and discontinuously at ${T}_{\text{IC}}\ensuremath{\approx}468$ K. Two lattice instabilities are present in the cubic phase: AFD instability with critical temperature ${T}_{0}\ensuremath{\approx}441$ K and ferroelectric instability with ${T}_{0}\ensuremath{\approx}408$ K. The IC instability is absent. The analysis of the transition mechanism within the Landau theory of coupled order parameters indicates that the transition is of triggered character, conditioned upon the attractive biquadratic coupling between the IC modulation and the AFD octahedral tilts, and is driven by the AFD soft mode.

Controversy in the description/identification of so-called intermediate phase(s) in PbHfO

The nature of precursor phenomena in the paraelectric phase of ferroelectrics is one of the main questions to be resolved from a fundamental point of view. Barium titanate (BaTiO3) is one of the most representative perovskite-structured ferroelectrics intensively studied until now. The pretransitional behavior of BaTiO3 single crystal grown using a solid-state crystal growth (SSCG) method was investigated for the first time and compared to previous results. There is no melting process in the SSCG method, thus the crystal grown using a SSCG method have inherent higher levels of impurity and defect concentrations, which is a good candidate for investigating the effect of crystal quality on the precursor phenomena. The acoustic, dielectric, and piezoelectric properties, as well as birefringence, of the SSCG-grown BaTiO3 were examined over a wide temperature range. Especially, the acoustic phonon behavior was investigated in terms of Brillouin spectroscopy, which is a complementary technique to Raman spectroscopy. The obtained precursor anomalies of the SSCG-grown BaTiO3 in the cubic phase were similar to those of other single crystals, in particular, of high-quality single crystal grown by top-seeded solution growth method. These results clearly indicate that the observed precursor phenomena are common and intrinsic effect irrespective of the crystal quality.

We have succeeded to grow single PbZr1-xTixO3 (PZT) crystal with Ti content of the order of x = 0.13. PZT compound with such Ti concentration is characterised by structural coexistence of the rhombohedral and monoclinic structures at each temperature below TC. It seems that investigations of the dielectric, piezoelectric and optical properties confirm this highly complicated co-existence.

The almost multiferroic perovskite EuTiO3 (ETO) has been prepared as films on substrates of SrTiO3. For all prepared film thicknesses highly transparent insulating films with atomically flat surfaces and excellent orientation have been grown. They were characterized by X-ray diffraction, magnetic susceptibility and birefringence measurements and found to exhibit bulk properties, namely an antiferromagnetic transition at TN = 5.1 K and a structural transition at TS = 282 K. The latter could only be identified due to the high transparency of the samples since the optical band gap is of the order of 4.5 eV and larger than observed before for any bulk and thin film samples.

Professor Ihor Stasyuk, a prominent scientist and lecturer passed away on 16 September 2019. He significantly contributed with remarkable results to the quantum many-body physics and to the theoret...