Large pyroelectric energy conversion in lead scandium tantalate thin films.

Non-linear pyroelectric energy harvesting using ferroelectric thin films exhibits high energy conversion, primarily due to their large breakdown field compared to bulks. Here, we report the pyroelectric energy conversion potential of lead scandium tantalate, Pb(Sc1/2Ta1/2)O3 (PST) thin film fabricated on a c-sapphire substrate using chemical solution deposition. To enable the application of high electric field and to assess the pyroelectric energy conversion performance, interdigitated electrodes were deposited on the PST thin film. A maximum harvested energy density of 9.1 J cm-3 per cycle was deduced from polarization measurements in films undergoing an Olsen cycle between 0 °C and 150 °C when the electric field was varied between 50 and 1500 kV/cm. Furthermore, PST thin films can reach up to 27 % of Carnot efficiency for a temperature interval of 10 K between 30 °C and 40 °C. This study highlights the significance of PST thin films for electro-thermal energy harvesting and promising opportunities for enhancing the conversion efficiency and power density using thin films or thin film multi-layer capacitors in the future for thermal energy harvesting.

High cooling performance in a double-loop electrocaloric heat pump.

Cooling through solid-state electrocaloric materials is an attractive replacement for vapor compression. Despite recent efforts, devices that are potentially commercially competitive have not been developed. We present an electrocaloric cooler with a maximum temperature span of 20.9 kelvin and a maximum cooling power of 4.2 watts under the moderate applied electric field of 10 volts per micrometer without any observed breakdown. Moreover, the maximum coefficient of performance, even taking into account energy expended on fluid pumping, reaches 64% of Carnot's efficiency as long as energy is properly recovered. We believe that this demonstration shows electrocaloric cooling to be a very promising alternative to vapor compression cooling.

Increasing bulk photovoltaic current by strain tuning.

Photovoltaic phenomena are widely exploited not only for primary energy generation but also in photocatalytic, photoelectrochemistry, or optoelectronic applications. In contrast to the interface-based photovoltaic effect of semiconductors, the anomalous or bulk photovoltaic effect in ferroelectrics is not bound by the Shockley-Queisser limit and, thus, can potentially reach high efficiencies. Here, we observe in the example of an Fe-doped LiNbO3 bulk single crystal the existence of a purely intrinsic "piezophotovoltaic" effect that leads to a linear increase in photovoltaic current density. The increase reaches 75% under a low uniaxial compressive stress of 10 MPa, corresponding to a strain of only 0.005%. The physical origin and symmetry properties of the effect are investigated, and its potential for strain-tuned efficiency increase in nonconventional photovoltaic materials is presented.

Unexpectedly high piezoelectricity of Sm-doped lead zirconate titanate in the Curie point region.

Large piezoelectric coefficients in polycrystalline lead zirconate titanate (PZT) are traditionally achieved through compositional design using a combination of chemical substitution with a donor dopant and adjustment of the zirconium to titanium compositional ratio to meet the morphotropic phase boundary (MPB). In this work, a different route to large piezoelectricity is demonstrated. Results reveal unexpectedly high piezoelectric coefficients at elevated temperatures and compositions far from the MPB. At temperatures near the Curie point, doping with 2 at% Sm results in exceptionally large piezoelectric coefficients of up to 915 pm/V. This value is approximately twice those of other donor dopants (e.g., 477 pm/V for Nb and 435 pm/V for La). Structural changes during the phase transitions of Sm-doped PZT show a pseudo-cubic phase forming ≈50 °C below the Curie temperature. Possible origins of these effects are discussed and the high piezoelectricity is posited to be due to extrinsic effects. The enhancement of the mechanism at elevated temperatures is attributed to the coexistence of tetragonal and pseudo-cubic phases, which enables strain accommodation during electromechanical deformation and interphase boundary motion. This work provides insight into possible routes for designing high performance piezoelectrics which are alternatives to traditional methods relying on MPB compositions.

Influence of defects and domain walls on dielectric and mechanical resonances in LiNbO3.

Monodomain and periodically poled LiNbO3 crystals (congruent composition) show dielectric and piezoelectric resonances between 100 K and 900 K. Dielectric measurements show resonances in some samples between 10-100 kHz. These resonances vanish under thermal anneal in monodomain crystals while they remain stable in periodically poled samples with high domain wall densities. The low activation energy of 0.18 eV suggests their electronic (bi-polaronic) origin. Resonant piezoelectric spectroscopy, RPS, shows two features in virgin samples: a relaxation peak at 420 K and a rapid hardening when the sample was slowly heated to ~500 K. The dynamic relaxation and the hardening are related to excitations and reorientations of Li defects. The relaxations and hardening are irreversibly suppressed by high temperature anneal. We do not observe domain wall related RPS resonances in annealed samples, which excludes the existence of highly charged walls. We suggest that domain walls stabilize polaronic states with (bi-)polarons located inside or near to the ferroelectric domain walls.

Electron paramagnetic resonance study of ZnO varistor material.

Matsuoka-type zinc oxide (ZnO) varistor material was synthesized using a conventional solid-state reaction method. X-band electron paramagnetic resonance (EPR) data revealed that Mn ions substitute in the ZnO lattice with a 2+ paramagnetic state. Co ions with either 3+ or 2+ oxidation states are only detectable at cryogenic temperatures. A Cr(3+) EPR signal was strongly suppressed or masked by a Mn(2+) signal. Photoluminescence and electrical results indicated that the varistor sample has fewer intrinsic defects and much higher resistivity as compared to undoped and metal-ion doped ZnO.

Effect of electrical and mechanical poling history on domain orientation and piezoelectric properties of soft and hard PZT ceramics.

The superior piezoelectric properties of all polycrystalline ferroelectrics are based on the extent of non-180° domain wall motion under electrical and mechanical poling loads. To distinguish between 180° and non-180° domain wall motion in a soft-doped and a hard-doped lead zirconate titanate (PZT) ceramic, domain texture measurements were performed using x-ray and neutron diffraction after different loading procedures. Comparing the results to measurements of the remanent strain and piezoelectric coefficient allowed the differentiation between different microstructural contributions to the macroscopic parameters. Both types of ceramic showed similar behavior under electric field, but the hard-doped material was more susceptible to mechanical load. A considerable fraction of the piezoelectric coefficient originated from poling by the preferred orientation of 180° domains.

Dielectric investigations of 0.945(Bi0.5Na0.5) TiO3-0.055BaTiO3.

Dielectric properties of 0.945(Bi(0.5)Na(0.5)) TiO(3)-0.055BaTiO(3)(BNBT5.5) (a composition close to the rhombohedral- tetragonal morphotropic phase boundary) ceramics are studied. It is shown that BNBT5.5 is a relaxor with a characteristic relaxation time that follows Vogel-Fulcher's law. The following Vogel-Fulcher parameters of the relaxation time were calculated: tau(0) = (2.0 +/- 2.4) x 10(-14) s, E/B(k) = (1620 +/- 270) K, Tau(0) = (262 +/- 9) K.