A new generation of solid-state photovoltaics is being made possible by the use of organometal-trihalide perovskite materials. While some of these materials are expected to be ferroelectric, almost nothing is known about their ferroelectric properties experimentally. Using piezoforce microscopy (PFM), here we show unambiguously, for the first time, the presence of ferroelectric domains in high-quality β-CH3NH3PbI3 perovskite thin films that have been synthesized using a new solution-processing method. The size of the ferroelectric domains is found to be about the size of the grains (∼100 nm). We also present evidence for the reversible switching of the ferroelectric domains by poling with DC biases. This suggests the importance of further PFM investigations into the local ferroelectric behavior of hybrid perovskites, in particular in situ photoeffects. Such investigations could contribute toward the basic understanding of photovoltaic mechanisms in perovskite-based solar cells, which is essential for the further enhancement of the performance of these promising photovoltaics.
Ferroelectric and ferroelastic domain structure has a profound effect on the piezoelectric, ferroelectric, and dielectric responses of ferroelectric materials. However, domain walls and strain field effects on thermal properties are unknown. We measured the thermal conductance from 100-400 K of epitaxially grown BiFeO 3 thin films with different domain variants, each separated primarily by 71 domain walls. We determined the Kapitza conductance across the domain walls, which is driven by the strain field induced by the domain variants. This domain wall Kapitza conductance is lower than the Kapitza conductance associated with grain boundaries in all previously measured materials.
Lateral subdivision of blanket piezoelectric thin films increases the functional properties through both increased domain wall mobility and declamping of the intrinsic response. This work presents the local effects of substrate declamping on the piezoelectric coefficient d 33,f of 300 nm thick, rhombohedral, {001}-oriented lead magnesium niobate-lead titanate thin films at the 70/30 composition (70PMN-30PT). Films grown by chemical solution deposition on platinized Si substrates are patterned into strip structures ranging from 0.75 to 9 µm in width. The longitudinal piezoelectric coefficient, d 33,f , is interrogated as a function of position across the patterned structures by three approaches: finite element modeling, piezoresponse force microscopy, and nanoprobe synchrotron X-ray diffraction. It is found that d 33,f increases from the clamped value of 40-50 to ≈160 pm V −1 at the free sidewall under 200 kV cm −1 excitation. The sidewalls partially declamp the piezoelectric response 500-600 nm into the patterned structure, raising the piezoelectric response at the center of features with lateral dimensions less than 1 µm (3:1 width to thickness aspect ratio). The normalized data from all three methods are in excellent agreement, with quantitative differences providing insight to the field dependence of the piezoelectric coefficient and its declamping behavior.
A mixed precursor solution method was used to deposit 3-0 nanocomposite thin films of PbZrTiO (PZT) and CoFeO (CFO). The piezoelectric behavior of PZT and magnetostrictive behavior of CFO allow for magnetoelectric (ME) coupling through strain transfer between the respective phases. High ME coupling is desired for many applications including memory devices, magnetic field sensors, and energy harvesters. The spontaneous phase separation in the 3-0 nanocomposite film was observed, with 25 nm CFO particle or nanophases distributed in discrete layers through the thickness of the PZT matrix. Magnetic-force microscopy images of the nanocomposite thin film under opposite magnetic poling conditions revealed in-plane pancake-like regions of higher concentration of the CFO nanoparticles. The constraints on the size and distribution of the CFO nanoparticles created a unique distribution in a PZT matrix and achieved values of ME coupling of 3.07 V cm Oe at a DC bias of 250 Oe and 1 kHz, increasing up to 25.0 V cm Oe at 90 kHz. Piezo-force microscopy was used to investigate the ferroelectric domain structure before and after opposite magnetic poling directions. It was found that in this nanocomposite, the polarization of the ferroelectric domains switched direction as a result of switching the direction of the magnetization by magnetic fields.
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