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A systematic study of (1−x)Pb(Fe0.5Nb0.5)O3–xBiFeO3 (x = 0–0.5) was performed by combining dielectric and electromechanical measurements with structural and microstructural characterization in order to investigate the strengthening of the relaxor properties when adding BiFeO3 into Pb(Fe0.5Nb0.5)O3 and forming a solid solution. Pb(Fe0.5Nb0.5)O3 crystalizes in monoclinic symmetry exhibiting ferroelectric-like polarization versus electric field (P–E) hysteresis loop and sub-micron-sized ferroelectric domains. Adding BiFeO3 to Pb(Fe0.5Nb0.5)O3 favors a pseudocubic phase and a gradual strengthening of the relaxor behavior of the prepared ceramics. This is indicated by a broadening of the peak in temperature-dependent permittivity, narrowing of P–E hysteresis loops and decreasing size of ferroelectric domains resulting in polar nanodomains for x = 0.20 composition. The relaxor behavior was additionally confirmed by Vogel–Fulcher analysis. For the x ≥ 0.30 compositions, broad high-temperature anomalies are observed in dielectric permittivity versus temperature measurements in addition to the frequency-dispersive peak located close to room temperature. These samples also exhibit pinched P–E hysteresis loops. The observed pinching is most probably related to the reorganization of polar nanoregions under the electric field as shown by synchrotron X-ray diffraction measurements as well as by piezo-response force microscopy analysis, while in part affected by the presence of charged point defects and anti-ferroelectric order, as indicated from rapid cooling experiments and high-resolution transmission electron microscopy, respectively.

For the first time, we demonstrated successful post-synthesis incorporation of metal dopants at elevated temperature into a host structure of Sn2P2S6, known as the grandfather of dichalcogenide ferroelectrics with a formula M2P2X6 (M = metal and X = chalcogen). With the example of Cu, we show that the integration of dopant atoms into the bulk of an already grown crystal could be easily tuned up to 0.5 at% affecting the structural, optical, vibrational, electrical, and ferroelectric properties. Thermally diffused copper atoms in Sn2P2S6 bulk are in the metallic state, inducing a multiaxial expansion of the Sn2P2S6 unit cell for 2–3.4%. The energy reduction between indirect and direct optical transitions was observed, combined by small hardening for acoustic and soft optical vibrational modes originating in the partial substitution of Sn by Cu in the Sn2P2S6 crystal lattice. Similar to hydrostatic pressure, the structurally bonded copper initiates a small downward shift in the critical temperature Tc. The presence of copper has a substantial impact on the shape smearing of the ferroelectric domains as well as on the behaviour of the dielectric permittivity. The real part of the dielectric constant e′ reaches its maximal value at intermediate concentrations of Cu 0% < x < 0.5%, showing an ∼20% increase with respect to the parent structure. The incorporated metal atoms provoke a monotonous expansion of the ferroelectric P–E loops along the increased dopant content direction. An increase in the electrical conductivity at higher Cu concentration reveals a trend for inducing a metal-like behaviour.

The search for new single-phase multicaloric materials, combining electrocaloric and magnetocaloric effects, is just at its beginning. Since the highest caloric effects are obtained near ferroic phase transitions, multiferroics with room-temperature ferroic anomalies are promising candidates for multicaloric cooling. In this work, such materials were prepared by tailoring the temperature of the ferroic anomalies by introducing BiFeO3, a material possessing high-temperature ferroic phase transitions, into the multicaloric Pb(Fe0.5Nb0.5)O3 to form a solid solution. A series of (1−x)Pb(Fe0.5Nb0.5)O3–xBiFeO3 (x = 0–0.5) were prepared. Among them, 0.8Pb(Fe0.5Nb0.5)O3–0.2BiFeO3 exhibits both dielectric permittivity and magnetic susceptibility anomalies at room temperature and is therefore one of the first such single-phase materials. However, at higher temperatures the material exhibits excessive Joule heating that critically degrades the electrocaloric cooling effect, while the antiferromagnetic nature of the material results in a low magnetocaloric response. Because of that, the multicaloric properties of 0.8Pb(Fe0.5Nb0.5)O3–0.2BiFeO3 were further improved by doping the material with Mn and Gd ions. This results in a composition with negligible Joule heating up to 75 °C and with room-temperature electrocaloric effect of more than 1 °C, and a high magnetocaloric effect of ∼3 °C at cryogenic temperatures. Furthermore, this material also exhibits the highest room-temperature magnetocaloric effect (∼8 × 10−3 °C) among all already known Pb(Fe0.5Nb0.5)O3-based multicalorics.