Strain effects have a significant role in mediating classic ferroelectric behavior such as polarization switching and domain wall dynamics. These effects are of critical relevance if the ferroelectric order parameter is coupled to strain and is therefore, also ferroelastic. Here, switching spectroscopy piezoresponse force microscopy (SS‐PFM) is combined with control of applied tip pressure to exert direct control over the ferroelastic and ferroelectric switching events, a modality otherwise unattainable in traditional PFM. As a proof of concept, stress‐mediated SS‐PFM is applied toward the study of polarization switching events in a lead zirconate titanate thin film, with a composition near the morphotropic phase boundary with co‐existing rhombohedral and tetragonal phases. Under increasing applied pressure, shape modification of local hysteresis loops is observed, consistent with a reduction in the ferroelastic domain variants under increased pressure. These experimental results are further validated by phase field simulations. The technique can be expanded to explore more complex electromechanical responses under applied local pressure, such as probing ferroelectric and ferroelastic piezoelectric nonlinearity as a function of applied pressure, and electro‐chemo‐mechanical response through electrochemical strain microscopy.

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Delivering foreign molecules into human cells is a wide and ongoing area of research. Gene therapy, or delivering nucleic acids into cells via nonviral or viral pathways, is an especially promising area for pharmaceutics. All gene therapy methods have their respective advantages and disadvantages, including limited delivery efficiency and low viability. We present an electromechanical method for delivering foreign molecules into human cells. Nanoinjection, or delivering molecules into cells using a solid lance, has proven to be highly efficient while maintaining high viability levels. This paper describes an array of solid silicon microlances that was tested to determine efficiency and viability when nanoinjecting tens of thousands of HeLa cells simultaneously. Propidium iodide (PI), a dye that fluoresces when bound to nucleic acids and does not fluoresce when unbound, was delivered into cells using the lance array. Results show that the lance array delivers PI into up to 78% of a nanoinjected HeLa cell culture, while maintaining 78-91 % viability. With these results, we submit the nanoinjection method using a silicon lance array as another promising particle delivery method for mammalian culture cells.

The effects of gamma irradiation on the dielectric and piezoelectric responses of Pb[Zr0.52Ti0.48]O3 (PZT) thin film stacks were investigated for structures with conductive oxide (IrO2) and metallic (Pt) top electrodes. The samples showed, generally, degradation of various key dielectric, ferroelectric, and electromechanical responses when exposed to 2.5 Mrad (Si) 60Co gamma radiation. However, the low-field, relative dielectric permittivity, εr, remained largely unaffected by irradiation in samples with both types of electrodes. Samples with Pt top electrodes showed substantial degradation of the remanent polarization and overall piezoelectric response, as well as pinching of the polarization hysteresis curves and creation of multiple peaks in the permittivity-electric field curves post irradiation. The samples with oxide electrodes, however, were largely impervious to the same radiation dose, with less than 5% change in any of the functional characteristics. The results suggest a radiation-induced change in the defect population or defect energy in PZT with metallic top electrodes, which substantially affects motion of internal interfaces such as domain walls. Additionally, the differences observed for stacks with different electrode materials implicate the ferroelectric–electrode interface as either the predominant source of radiation-induced effects (Pt electrodes) or the site of healing for radiation-induced defects (IrO2 electrodes).

The ability to tailor the performance of functional materials, such as semiconductors, via careful manipulation of defects has led to extraordinary advances in microelectronics. Functional metal oxides are no exception – protonic-defect-conducting oxides find use in solid oxide fuel cells (SOFCs) and oxygen-deficient high-temperature superconductors are poised for power transmission and magnetic imaging applications. Similarly, the advantageous functional responses in ferroelectric materials that make them attractive for use in microelectromechanical systems (MEMS), logic elements, and environmental energy harvesting, are derived from interactions of defects with other defects (such as domain walls) and with the lattice. Chemical doping has traditionally been employed to study the effects of defects in functional materials, but complications arising from compositional heterogeneity often make interpretation of results difficult. Alternatively, irradiation is a versatile means of evaluating defect interactions while avoiding the complexities of doping. Here, a generalized phenomenological model is developed to quantify defect interactions and compare material performance in functional oxides as a function of radiation dose. The model is demonstrated with historical data from literature on ferroelectrics, and expanded to functional materials for SOFCs, mixed ionic-electronic conductors (MIECs), He-ion implantation, and superconductors. Experimental data is used to study microstructural effects on defect interactions in ferroelectrics.

This work investigates the role of microstructure on radiation-induced changes to the functional response of ferroelectric thin films. Chemical solution-deposited lead zirconate titanate thin films with columnar and equiaxed grain morphologies are exposed to a range of gamma radiation doses up to 10 Mrad and the resulting trends in functional response degradation are quantified using a previously developed phenomenological model. The observed trends of global degradation as well as local rates of defect saturation suggest strong coupling between ferroelectric thin film microstructure and material radiation hardness. Radiation-induced degradation of domain wall motion is thought to be the major contributor to the reduction in ferroelectric response. Lower rates of defect saturation are noted in samples with columnar grains, due to increased grain boundary density offering more sites to act as defect sinks, thus reducing the interaction of defects with functional material volume within the grain interior. Response trends for measurements at low electric field show substantial degradation of polarization and piezoelectric properties (up to 80% reduction in remanent piezoelectric response), while such effects are largely diminished at increased electric fields, indicating that the defects created/activated are primarily of low pinning energy. The correlation of film microstructure to radiation-induced changes to the functional response of ferroelectric thin films can be leveraged to tune and tailor the eventual properties of devices relying on these materials.

This work investigates the role of crystallization interfaces and chemical heterogeneity in the radiation tolerance of chemical solution-deposited lead zirconate titanate (PZT) thin films. Two sets of PZT thin films were fabricated with crystallization performed at (i) every deposited layer or (ii) every three layers. The films were exposed to a range of 60Co gamma radiation doses, between 0.2 and 20 Mrad, and their functional response was compared before and after irradiation. The observed trends indicate enhancements of dielectric, ferroelectric, and piezoelectric responses at low radiation doses and degradation of the same at higher doses. Response enhancements are expected to result from low-dose (≤2 Mrad), ionizing radiation-induced charging of internal interfaces—an effect that results in neutralization of pre-existing internal bias in the samples. At higher radiation doses (>2 Mrad), accumulation and self-ordering of radiation-modified, mobile, oxygen vacancy-related defects contribute to degradation of dielectric, ferroelectric, and piezoelectric properties, exacerbated in the samples with more crystallization layers, potentially due to increased defect accumulation at these internal interfaces. These results suggest that the interaction between radiation and crystallization interfaces is multifaceted—the effects of ionization, domain wall motion, point defect mobility, and microstructure are considered.

This work investigates the role of Mn-doping of ferroelectric lead zirconate titanate (PZT) thin films exposed to a range of ionizing radiation doses. PZT thin films were fabricated with both undoped and 4% Mn-doped compositions, and the functional response was compared both before and after exposure to gamma radiation doses up to 10 Mrad. A phenomenological model was applied to quantify defect interactions and compare trends in the degradation of the functional response. Mn-doped PZT samples demonstrate reduced magnitude of functional response in non-irradiated samples but exhibit vastly superior radiation tolerance of dielectric and ferroelectric properties across the range of gamma doses studied here. Strong MnZr/Ti″−VO·· defect dipoles pin domain walls, resulting in a lower initial functional response and mitigating the deleterious effects of irradiation on extrinsic contributions to the said response. Piezoelectric response trends as a function of radiation dose are highly nonlinear. The results of this work can be leveraged to engineer next-generation radiation-tolerant ferroelectric materials for applications where high levels of functional response stability are required, especially at elevated ionizing radiation dose.