Controlling polarization direction in epitaxial Pb(Zr0.2Ti0.8)O3 films through Nb (n-type) and Fe (p-type) doping

Fe (acceptor) and Nb (donor) doped epitaxial Pb(Zr0.2Ti0.8)O3 (PZT) films were grown on single crystal SrTiO3 substrates and their electric properties were compared to those of un-doped PZT layers deposited in similar conditions. All the films were grown from targets produced from high purity precursor oxides and the doping was in the limit of 1% atomic in both cases. The remnant polarization, the coercive field and the potential barriers at electrode interfaces are different, with lowest values for Fe doping and highest values for Nb doping, with un-doped PZT in between. The dielectric constant is larger in the doped films, while the effective density of charge carriers is of the same order of magnitude. An interesting result was obtained from piezoelectric force microscopy (PFM) investigations. It was found that the as-grown Nb-doped PZT has polarization orientated upward, while the Fe-doped PZT has polarization oriented mostly downward. This difference is explained by the change in the conduction type, thus in the sign of the carriers involved in the compensation of the depolarization field during the growth. In the Nb-doped film the majority carriers are electrons, which tend to accumulate to the growing surface, leaving positively charged ions at the interface with the bottom SrRuO3 electrode, thus favouring an upward orientation of polarization. For Fe-doped film the dominant carriers are holes, thus the sign of charges is opposite at the growing surface and the bottom electrode interface, favouring downward orientation of polarization. These findings open the way to obtain p-n ferroelectric homojunctions and suggest that PFM can be used to identify the type of conduction in PZT upon the dominant direction of polarization in the as-grown films.

As-Grown Domain Structure in Calcium Orthovanadate Crystals

An as-grown domain structure in nominally pure and Mn-doped calcium orthovanadate (CVO) crystals was studied by several methods of domain imaging: optical microscopy, piezoelectric force microscopy, and Cherenkov-type second harmonic generation. The combination of imaging methods provided an opportunity for comprehensive study of the domain structure on the polar surface and in the bulk of the samples. It was shown that, in nominally pure CVO crystals, an irregular 3D maze of rounded domains, with charged walls, essentially tilted from the polar direction, was present. It was proposed that the domain structure was formed just below the phase transition temperature and persisted during subsequent cooling. Such behavior is due to effective bulk screening of the depolarization field and a low value of the pyroelectric field which appears during cooling. The revealed formation of triangular domains and flat fragments of domain walls in Mn-doped CVO was attributed to polarization reversal under the action of the polar component of the pyroelectric field, above the threshold value for domain switching. This fact represents the first observation of the domain switching in CVO crystals.

Atomic Force Microscopy of the Local Electrical Properties of Bilayer Polyaniline-Polystyrene/P(VDF-TrFE) Composite

Atomic force microscopy techniques (conductive-AFM, I-V spectroscopy and PFM) were used for characterisation of the local electrical properties of bilayer polyaniline-polystyrene/P(VDF-TrFE) polymer nanocomposite. Observed hysteresis of current-voltage characteristics confirms its memristive properties. It was caused by the influence of the ferroelectric polarization of P(VDF-TrFE) layer, the domain structure of which was visualised by piezoelectric force microscopy on the transport of charge carriers at the interface.

Polarization-switching pathway determined electrical transport behaviors in rhombohedral BiFeO3 thin films

We investigate the polarization-switching pathway dependent electrical transport behaviors in rhombohedral-phase BiFeO3 thin films with a point contact geometry. By combining conducting-atomic force microscopy and piezoelectric force microscopy, we simultaneously...

Crack resistance of bismuth ferrite films obtained on a flexible substrate

Ultrathin BiOx and FeOx layers were obtained by Atomic Layer Deposition (ALD) on the surface of a flexible Kapton substrate (poly (4,4’-oxydiphenylene-pyromellitimide)) at a temperature of 250 °C. The layer thickness was 50 - 100 nm. Surface morphology, electrical polarization, and mechanical properties were investigated by Atomic Force Microscope, Piezoelectric Force Microscopy and Force Modulation Microscopy. Chemical analysis was performed by X-ray Photoelectron Spectroscopy, where the formation of Bi2O3 and Fe2O3 phases, as well as intermediate phases in the Bi-Fe-O system, was observed. With a small increase in the Bi content of the film, the BFO / Kapton structure becomes more crack resistant. Modification of the Kapton surface with bismuth and iron oxides showed that such a composition exhibits multiferroic behavior.

Ultrahigh Electromechanical Coupling and Its Thermal Stability in (Na1/2Bi1/2)TiO3-Based Lead-Free Single Crystals

In this work, we report the ultrahigh electromechanical coupling performance of NBT-6BT-KNN lead-free single crystal at room temperature. The thickness mode electromechanical coupling coefficient (kt) and the 31 mode electromechanical coupling coefficient (k31) reach 69.0% and 45.7%, respectively, which are superior to the PZT-5H lead-based ceramics of kt~60% and k31~39%. In addition, the evolution of the crystal structure and domain morphology is revealed by Raman scattering spectra, a polarizing microscope and piezoelectric force microscopy characterization.

Piezoelectric BiFeO3 Thin Films: Optimization of MOCVD Process on Si

This paper presents a simple and optimized metal organic chemical vapor deposition (MOCVD) protocol for the deposition of perovskite BiFeO3 films on silicon-based substrates, in order to move toward the next generation of lead-free hybrid energy harvesters. A bi-metal mixture that is composed of Bi(phenyl)3, and Fe(tmhd)3 has been used as a precursor source. BiFeO3 films have been grown by MOCVD on IrO2/Si substrates, in which the conductive IrO2 functions as a bottom electrode and a buffer layer. BiFeO3 films have been analyzed by X-ray diffraction (XRD) for structural characterization and by field-emission scanning electron microscopy (FE-SEM) coupled with energy dispersive X-ray (EDX) analysis for the morphological and chemical characterizations, respectively. These studies have shown that the deposited films are polycrystalline, pure BiFeO3 phase highly homogenous in morphology and composition all over the entire substrate surface. Piezoelectric force microscopy (PFM) and Piezoelectric Force Spectroscopy (PFS) checked the piezoelectric and ferroelectric properties of the film.

Quantitative analysis of the direct piezoelectric response of bismuth ferrite films by scanning probe microscopy

Polarisation domain structure is a microstructure specific to ferroelectrics and plays a role in their various fascinating characteristics. The piezoelectric properties of ferroelectrics are influenced by the domain wall contribution. This study provides a direct observation of the contribution of domain walls to the direct piezoelectric response of bismuth ferrite (BiFeO3) films, which have been widely studied as lead-free piezoelectrics. To achieve this purpose, we developed a scanning probe microscopy-based measurement technique, termed direct piezoelectric response microscopy (DPRM), to observe the domain structure of BiFeO3 films via the direct piezoelectric response. Quantitative analysis of the direct piezoelectric response obtained by DPRM, detailed analysis of the domain structure by conventional piezoelectric force microscopy, and microscopic characterisation of the direct piezoelectric properties of BiFeO3 films with different domain structures revealed that their direct piezoelectric response is enhanced by the walls between the domains of spontaneous polarisation in the same out-of-plane direction.