Enhancement of the Piezocatalytic Response of La-Doped BiFeO3 Nanoparticles by Defects Synergy.

Because of their intrinsic polarization and related properties, ferroelectrics attract significant attention to address energy transformation and environmental protection. Here, by using trivalent-ion-lanthanum doping of BiFeO3 nanoparticles (NPs), it is shown that defects and piezoelectric potential are synergized to achieve a high piezocatalytic effect for decomposing the model Rhodamine B (RhB) pollutant, reaching a record-high piezocatalytic rate of 21 360 L mol-1 min-1 (i.e., 100% RhB degradation within 20 min) that exceeds most state-of-the art ferroelectrics. The piezocatalytic Bi0.99La0.01FeO3 NPs are also demonstrated to be versatile toward various pharmaceutical pollutants with over 90% removal efficiency, making them extremely efficient piezocatalysts for water purification. It is also shown that 1% La-doping introduces oxygen vacancies and Fe2+ defects. It is thus suggested that oxygen vacancies act as both active sites and charge providers, permitting more surface adsorption sites for the piezocatalysis process, and additional charges and better energy transfer between the NPs and surrounding molecules. Furthermore, the oxygen vacancies are proposed to couple to Fe2+ to form defect dipoles, which in turn introduces an internal field, resulting in more efficient charge de-trapping and separation when added to the piezopotential. This synergistic mechanism is believed to provide a new perspective for designing future piezocatalysts with high performance.

High Electrocaloric Effect in Lead Scandium Tantalate Thin Films with Interdigitated Electrodes.

Lead scandium tantalate, Pb(Sc,Ta)O3, is an excellent electrocaloric material showing large temperature variations, good efficiency, and a broad operating temperature window. In form of multilayer ceramic capacitors integrated into a cooling device, the device can generate a temperature difference larger than 13 K. Here, we investigate Pb(Sc,Ta)O3 in form of thin films prepared using the sol-gel chemical solution deposition method. We report the detailed fabrication process of high-quality films on various substrates such as c-sapphire and fused silica. The main originality of this research is the use of interdigitated top electrodes, enabling the application of very large electric fields in PST. We provide structural and electrical characterisation, as well as electrocaloric temperature variation, using the Maxwell relation approach. Films do not show a B-site ordering. The temperature variation from 7.2 to 15.7 K was measured on the Pb(Sc,Ta)O3 film on a c-sapphire substrate under the electric field of 1330 kV/cm between 14.5 °C and 50 °C. This temperature variation is the highest reported so far in Pb(Sc,Ta)O3 thin films. Moreover, stress seems to have an effect on the maximum permittivity temperature and thus electrocaloric temperature variation with temperature in Pb(Sc,Ta)O3 films. Tensile stress induced by fused silica shifts the "transition" of Pb(Sc,Ta)O3 to lower temperatures. This study shows the possibility for electrocaloric temperature variation tuning with stress conditions.

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.

Crystallization of piezoceramic films on glass via flash lamp annealing.

Integration of thin-film oxide piezoelectrics on glass is imperative for the next generation of transparent electronics to attain sensing and actuating functions. However, their crystallization temperature (above 650 °C) is incompatible with most glasses. We developed a flash lamp process for the growth of piezoelectric lead zirconate titanate films. The process enables crystallization on various types of glasses in a few seconds only. The functional properties of these films are comparable to the films processed with standard rapid thermal annealing at 700 °C. A surface haptic device was fabricated with a 1 µm-thick film (piezoelectric e33,f of -5 C m-2). Its ultrasonic surface deflection reached 1.5 µm at 60 V, sufficient for its use in surface rendering applications. This flash lamp annealing process is compatible with large glass sheets and roll-to-roll processing and has the potential to significantly expand the applications of piezoelectric devices on glass.

Study of Gallium-Doped Zinc Oxide Thin Films Processed by Atomic Layer Deposition and RF Magnetron Sputtering for Transparent Antenna Applications.

Gallium-doped zinc oxide (GZO) films were fabricated using RF magnetron sputtering and atomic layer deposition (ALD). The latter ones demonstrate higher electrical conductivities (up to 2700 S cm-1) and enhanced charge mobilities (18 cm2 V-1 s-1). The morphological analysis reveals differences mostly due to the very different nature of the deposition processes. The film deposited via ALD shows an increased transmittance in the visible range and a very small one in the infrared range that leads to a figure of merit of 0.009 Ω-1 (10 times higher than for the films deposited via sputtering). A benchmarking is made with an RF sputtered indium-doped tin oxide (ITO) film used conventionally in the industry. Another comparison between ZnO, Al:ZnO (AZO), and Ga:ZnO (GZO) films fabricated by ALD is presented, and the evolution of physical properties with doping is evidenced. Finally, we processed GZO thin films on a glass substrate into patterned transparent patch antennas to demonstrate an application case of short-range communication by means of the Bluetooth Low Energy (BLE) protocol. The GZO transparent antennas' performances are compared to a reference ITO antenna on a glass substrate and a conventional copper antenna on FR4 PCB. The results highlight the possibility to use the transparent GZO antenna for reliable short-range communication and the achievability of an antenna entirely processed by ALD.

Quantification of the Electromechanical Measurements by Piezoresponse Force Microscopy.

Piezoresponse force microscopy (PFM) is widely used for characterization and exploration of the nanoscale properties of ferroelectrics. However, quantification of the PFM signal is challenging due to the convolution of various extrinsic and intrinsic contributions. Although quantification of the PFM amplitude signal has received considerable attention, quantification of the PFM phase signal has not been addressed. A properly calibrated PFM phase signal can provide valuable information on the sign of the local piezoelectric coefficient-an important and nontrivial issue for emerging ferroelectrics. In this work, two complementary methodologies to calibrate the PFM phase signal are discussed. The first approach is based on using a standard reference sample with well-known independently measured piezoelectric coefficients, while the second approach exploits the electrostatic sample-cantilever interactions to determine the parasitic phase offset. Application of these methodologies to studies of the piezoelectric behavior in ferroelectric HfO2 -based thin-film capacitors reveals intriguing variations in the sign of the longitudinal piezoelectric coefficient, d33,eff . It is shown that the piezoelectric properties of the HfO2 -based capacitors are inherently sensitive to their thickness, electrodes, as well as deposition methods, and can exhibit wide variations including a d33,eff sign change within a single device.

Piezoelectricity in hafnia.

Because of its compatibility with semiconductor-based technologies, hafnia (HfO2) is today's most promising ferroelectric material for applications in electronics. Yet, knowledge on the ferroic and electromechanical response properties of this all-important compound is still lacking. Interestingly, HfO2 has recently been predicted to display a negative longitudinal piezoelectric effect, which sets it apart from classic ferroelectrics (e.g., perovskite oxides like PbTiO3) and is reminiscent of the behavior of some organic compounds. The present work corroborates this behavior, by first-principles calculations and an experimental investigation of HfO2 thin films using piezoresponse force microscopy. Further, the simulations show how the chemical coordination of the active oxygen atoms is responsible for the negative longitudinal piezoelectric effect. Building on these insights, it is predicted that, by controlling the environment of such active oxygens (e.g., by means of an epitaxial strain), it is possible to change the sign of the piezoelectric response of the material.

Transparent Ferroelectric Capacitors on Glass.

We deposited transparent ferroelectric lead zirconate titanate thin films on fused silica and contacted them via Al-doped zinc oxide (AZO) transparent electrodes with an interdigitated electrode (IDE) design. These layers, together with a TiO2 buffer layer on the fused silica substrate, are highly transparent (>60% in the visible optical range). Fully crystallized Pb(Zr0.52Ti0.48)O3 (PZT) films are dielectrically functional and exhibit a typical ferroelectric polarization loop with a remanent polarization of 15 µC/cm². The permittivity value of 650, obtained with IDE AZO electrodes is equivalent to the one measured with Pt electrodes patterned with the same design, which proves the high quality of the developed transparent structures.