V. V. Shvartsman

Diffuse phase transition in BaTi1−xSnxO3 ceramics: An intermediate state between ferroelectric and relaxor behavior

Dielectric relaxation and polar structures of BaTi1−xSnxO3 ceramics, x=0.10–0.20, are investigated by means of dielectric spectroscopy and piezoresponse force microscopy. A transition regime between “normal” ferroelectric and relaxor behaviors is encountered. In the compositions with x=0.10, a complex domain pattern confirming the ferroelectric state is observed. Strong dielectric relaxation around Tm is attributed to domain wall motion. On the other hand, the dielectric spectra in the sample with x=0.20 are very similar to those observed in relaxor ferroelectrics. Analysis of the relaxation spectra at the intermediate concentration, x=0.15, reveals both domain wall response and an additional contribution related to mesoscale polar structures. The appearance of relaxor behavior in BaTi1−xSnxO3 is discussed within the framework of the random field model.

Crystal structure and multiferroic properties of Gd-substituted BiFeO3

Room-temperature crystal structure, local ferroelectric, and magnetic properties of the Bi1−xGdxFeO3 (x=0.1,0.2,0.3) polycrystalline samples have been investigated by x-ray diffraction, piezoresponse force microscopy, and magnetometry techniques. Performed measurements have revealed a sequence of the composition-driven structural phase transitions R3c→Pn21a (occurs at x∼0.1) and Pn21a→Pnma (takes place within the concentrational range of 0.2<x<0.3). The latter structural transformation is attributed to the substitution-induced suppression of the polar displacements. Gd substitution has been shown to effectively induce the appearance of the spontaneous magnetization, thus indicating a promising way for improving multiferroic properties of antiferromagnetic BiFeO3.

Domain populations in lead zirconate titanate thin films of different compositions via piezoresponse force microscopy

Pb (ZrxTi1−x)O3 (PZT) thin films with (111) texture were deposited onto commercially available Pt/Ti/SiO2/Si substrates via the sol–gel technique. Piezoforce microscopy (PFM) was then used to analyse the evolution of domain populations as a function of the Zr content x. Domain structures of virgin films, local piezoelectric properties of individual grains and piezoelectric histograms were studied in films with different compositions (x = 0.2–0.6), which cover both the tetragonal and rhombohedral sides of the phase diagram. In films with low Zr content mainly single-domain grains were observed. As the Zr content increased, a larger fraction of polydomain grains was found. The local piezoelectric response measured inside sufficiently big grains indicated that the strongest piezoelectric effect occurs in PZT30/70 (x = 0.3) films. This was attributed to two different effects: high out-of-plane polarization achieved due to the (111) texture and influence of the dielectric constant. In tetragonal films with their lower dielectric constants the electric field seen by a ferroelectric is higher as compared to other compositions, giving rise to an apparent increase of the effective piezoelectric response measured by PFM. The analysis of the domain images indicated that sol–gel derived PZT films are slightly self-polarized near the free surface. With increasing Zr/Ti ratio, the variation of domain populations resulted in reversing the sign of the average piezoelectric response at x≈0.3. It is demonstrated that PFM histograms are extremely sensitive to PZT composition and can be used as a signature of complex domain structures in ferroelectric thin films.

Nanoscale domains and local piezoelectric hysteresis in Pb(Zn1/3Nb2/3)O3-4.5%PbTIO3 single crystals

High-resolution domain studies have been performed in Pb(Zn1/3Nb2/3)O3-4.5%PbTiO3 (PZN-PT) single crystals via piezoresponse force microscopy (PFM). Irregular domain patterns with the typical sizes 20–100 nm have been observed on the (001)-oriented surfaces of unpoled samples. On the contrary, (111) crystal cuts exhibit normal micron-sized regular domains with the domain boundaries directed along allowed crystallographic planes. The existence of nanodomains in (001)-oriented crystals is tentatively attributed to the relaxor nature of PZN-PT where small polar clusters may form under zero-field-cooling conditions. These nanodomains are considered as the nuclei of the opposite polarization state and can be responsible for the smaller coercive field for this particular crystal cut. However, local piezoelectric hysteresis performed by PFM on the nanometer scale indicates similar switching behavior of PZN-PT for both investigated crystallographic orientations.

Anomalous polarization inversion in ferroelectrics via scanning force microscopy

Local poling of ferroelectrics by the sharp conducting tip of a scanning force microscope (SFM) is studied experimentally and theoretically. The formation of the inverse domain under the SFM tip, where the polarization is oriented in the direction opposite to that of the poling field, is reported for bulk ferroelectrics (single crystals of solid solutions PbZn1/3Nb2/3O3–PbTiO3). This finding confirms earlier results on ferroelectric thick films, thus proving the universality of the anomalous polarization inversion in ferroelectric media. It is shown that the inverse domain grows with the increase of the poling voltage and duration and remains stable for a long time after the removal of electric field. The growth process is described by a dynamic model assuming that the appearance of inverse domains is due to a local internal electric field directed against the poling one. This field is attributed to the space charge formed beneath the SFM tip due to injection of charge carriers and their subsequent drift and trapping. Poling voltage and poling time dependences of the domain size are correctly described by the model. Implications of the anomalous polarization inversion for the domain engineering and dense data storage in ferroelectrics are discussed.

Polar nanodomains and local ferroelectric phenomena in relaxor lead lanthanum zirconate titanate ceramics

Transparent Pb0.9125La0.0975(Zr0.65Ti0.35)0.976O3 ceramics (conventionally abbreviated as PLZT 9.75/65/35) is a typical relaxor characterized by the absence of the ferroelectric order at the macroscopic scale. In this letter, we report on the observation of complex polar structures on the surface of this material via piezoresponse force microscopy (PFM). The irregular polarization patterns are associated with the formation of a glassy state, where random electric fields destroy the long-range ferroelectric order. The measure of the disorder, the correlation length of ∼50nm, was directly deduced from the PFM images. Local poling of relaxor ceramics resulted in the formation of a stable micron-size domain that could be continuously switched under varying dc bias (local relaxor-ferroelectric phase transition). Fractal analysis was applied to analyze the origin of local order in PLZT.

Stress-induced suppression of piezoelectric properties in PbTiO3:La thin films via scanning force microscopy

Sol-gel derived polycrystalline La-doped PbTiO3 films are investigated by scanning force microscopy (SFM) in a piezoelectric contact mode. The SFM signal proportional to the effective piezoelectric coefficient, deff, is measured inside individual domains as a function of the mechanical force exerted by the SFM tip on the film’s surface. It is found that the piezoelectric signal can be fully suppressed under sufficiently high force (∼20–22 μN). The suppression is qualitatively different for domains of opposite polarities where deff may change its sign depending on the orientation of polarization vector. The piezoelectric hysteresis loops acquired under increasing force gradually shrink with an asymmetric decrease of the piezoelectric coefficients. This leads to a pronounced vertical shift of the loops (deff offset). The obtained results are discussed in terms of the competing electrostatic and piezoelectric contributions to the measured signal and stress-induced polarization instabilities in the vicinity o...

Nonlinear local piezoelectric deformation in ferroelectric thin films studied by scanning force microscopy

Local piezoelectric deformation is investigated in (Pb,La)TiO3 (PLT) and Pb(Zr,Ti)O3 (PZT) thin films via scanning force microscopy (SFM) as a function of the ac voltage Vac applied between the conducting tip and the bottom electrode. Thus obtained voltage dependence of the effective piezoelectric coefficient (local piezoelectric nonlinearity) is compared with the corresponding macroscopic piezoelectric behavior determined by laser interferometry. As expected, the local piezoresponse of PLT films measured inside uniformly polarized areas (ferroelectric domains) remains almost linear with increasing Vac until the driving voltage becomes comparable with the coercive one. The corresponding macroscopic response is substantially nonlinear, suggesting significant contribution from the motion of 90° domain walls. On the contrary, in PZT films the local piezoelectric behavior is strongly nonlinear, whereas the macroscopic piezoelectric coefficient is almost field independent. Moreover, depending on the polarity o...

Strong electrocaloric effect in lead-free 0.65Ba(Zr0.2Ti0.8)O3-0.35(Ba0.7Ca0.3)TiO3 ceramics obtained by direct measurements

Solid solutions of (1 − x)Ba(Zr0.2Ti0.8)O3-x(Ba0.7Ca0.3)TiO3 promise to exhibit a large electrocaloric effect (ECE), because their Curie temperature and a multiphase coexistence region lie near room temperature. We report on direct measurements of the electrocaloric effect in bulk ceramics 0.65Ba(Zr0.2Ti0.8)O3-0.35(Ba0.7Ca0.3)TiO3 using a modified differential scanning calorimeter. The adiabatic temperature change reaches a value of ΔTEC = 0.33 K at ∼65 °C under an electric field of 20 kV/cm. It remains sizeable in a broad temperature interval above this temperature. Direct measurements of the ECE proved that the temperature change exceeds the indirect estimates derived from Maxwell relations by about ∼50%. The discrepancy is attributed to the relaxor character of this material.

Crossover from ferroelectric to relaxor behavior in BaTi1− x Sn x O3 solid solutions

Dielectric relaxation of BaTi1− x Sn x O3 ceramics is investigated by means of dielectric spectroscopy. The gradual crossover from ferroelectric to relaxor behavior is characterized by vanishing of the contribution due to domain walls and appearance of relaxation related to reorientation of polar nanosized regions. Typical behavior of relaxors is observed only in ceramics with x = 0.30, while the compositions with 0.175 ≤ x ≤ 0.25 show coexistence of both ferroelectric and relaxor features. The relaxor properties are supposed to be due to both weak random fields and disorder inherent in pure BaTiO3.