We investigate the ferroelectric properties of photovoltaic methylammonium lead halide CH3NH3PbI3 perovskite using piezoelectric force microscopy (PFM) and macroscopic polarization methods. The electric polarization is clearly observed by amplitude and phase hysteresis loops. However, the polarization loop decreases as the frequency is lowered, persisting for a short time only, in the one second regime, indicating that CH3NH3PbI3 does not exhibit permanent polarization at room temperature. This result is confirmed by macroscopic polarization measurement based on a standard capacitive method. We have observed a strong increase of piezoelectric response under illumination, consistent with the previously reported giant photoinduced dielectric constant at low frequencies. We speculate that an intrinsic charge transfer photoinduced dipole in the perovskite cage may lie at the origin of this effect.

Poly(ethylene oxide) is demonstrated to be a suitable matrix polymer for the solution‐doped conjugated polymer poly(3‐hexylthiophene). The polarity of the insulator combined with carefully chosen processing conditions permits the fabrication of tens of micrometer‐thick films that feature a fine distribution of the F4TCNQ dopant:semiconductor complex. Changes in electrical conductivity from 0.1 to 0.3 S cm−1 and Seebeck coefficient from 100 to 60 μV K−1 upon addition of the insulator correlate with an increase in doping efficiency from 20% to 40% for heavily doped ternary blends. An invariant bulk thermal conductivity of about 0.3 W m−1 K−1 gives rise to a thermoelectric Figure of merit ZT ∼ 10−4 that remains unaltered for an insulator content of more than 60 wt%. Free‐standing, mechanically robust tapes illustrate the versatility of the developed dopant:semiconductor:insulator ternary blends.

Bacteria are used to grow in an aqueous medium a cellulose-carbon nanotube composite porous film with good thermoelectric properties, flexibility and recyclability.

No abstract

We employ direct piezoelectric force microscopy to examine the ferroelectric response of halide perovskites and prove that halide perovskites are ferroelectricity free.

While piezoelectric and ferroelectric materials play a key role in many everyday applications, there are still a number of open questions related to their physics. To enhance our understanding of piezoelectrics and ferroelectrics, nanoscale characterization is essential. Here, we develop an atomic force microscopy based mode that obtains a direct quantitative analysis of the piezoelectric coefficient d33. We report nanoscale images of piezogenerated charge in a thick single crystal of periodically poled lithium niobate (PPLN), a bismuth ferrite (BiFO3) thin film, and lead zirconate titanate (PZT) by applying a force and recording the current produced by these materials. The quantification of d33 coefficients for PPLN (14 ± 3 pC per N) and BFO (43 ± 6 pC per N) is in agreement with the values reported in the literature. Even stronger evidence of the reliability of the method is provided by an equally accurate measurement of the significantly larger d33 of PZT.

Piezoresponse Force Microscopy is a powerful but delicate nanoscale technique that measures the mechanical response resulting from the application of a highly localized electric field. Though mechanical response is normally due to piezoelectricity, other physical phenomena, especially electrostatic interaction, can contribute to the signal read. We address this problematic through the use of longer ultra-stiff probes providing state of the art sensitivity, with the lowest electrostatic interaction and avoiding working in high frequency regime. In order to find this solution we develop a theoretical description addressing the effects of electrostatic contributions in the total cantilever vibration and its quantification for different setups. The theory is subsequently tested in a Periodically Poled Lithium Niobate (PPLN) crystal, a sample with well-defined 0º and 180º domains, using different commercial available conductive tips. We employ the theoretical description to compare the electrostatic contribution effects into the total phase recorded. Through experimental data our description is corroborated for each of the tested commercially available probes. We propose that a larger probe length can be a solution to avoid electrostatic forces, so the cantilever-sample electrostatic interaction is reduced. For hard oxide samples we propose an ultra-stiff cantilever which avoids the use of high frequency voltage but still diminishing electrostatic forces. Our proposed commercially available solution have great implications into avoiding artifacts while studying soft biological samples, multiferroic oxides, and thin film ferroelectric materials and it opens a new window into tip engineering.

Highly crystalline epitaxial Ba0.8Sr0.2TiO3 (BST) thin-films are grown on (001)-oriented LaNiO3-buffered LaAlO3 substrates by pulsed laser irradiation of solution derived barium-zirconium-titanium precursor layers using a UV Nd:YAG laser source at atmospheric conditions. The structural analyses of the obtained films, studied by X-ray diffractometry and transmission electron microscopy, demonstrate that laser processing allows the growth of tens of nm-thick BST epitaxial films with crystalline structure similar to that of films obtained through conventional thermal annealing methods. However, the fast pulsed nature of the laser employed leads to crystallization kinetic evolution orders of magnitude faster than in thermal treatments. The combination of specific photothermal and photochemical mechanisms is the main responsible for the ultrafast epitaxial laser-induced crystallization. Piezoresponse microscopy measurements demonstrate equivalent ferroelectric behavior in laser and thermally annealed films, being the piezoelectric constant ∼25 pm V−1.