The Formation of Self-Organized Domain Structures at Non-Polar Cuts of Lithium Niobate as a Result of Local Switching by an SPM Tip

We have studied experimentally the interaction of isolated needle-like domains created in an array via local switching using a biased scanning probe microscope (SPM) tip and visualized via piezoelectric force microscopy (PFM) at the non-polar cuts of MgO-doped lithium niobate (MgOLN) crystals. It has been found that the domain interaction leads to the intermittent quasiperiodic and chaotic behavior of the domain length in the array in a manner similar to that of polar cuts, but with greater spacing between the points of bias application and voltage amplitudes. It has also been found that the polarization reversal at the non-polar cuts and domain interaction significantly depend on humidity. The spatial distribution of the surface potential measured by Kelvin probe force microscopy in the vicinity of the charged domain walls revealed the decrease of the domain length as a result of the partial backswitching after pulse termination. The phase diagram of switching behavior as a function of tip voltage and spacing between the points of bias application has been plotted. The obtained results provide new insight into the problem of the domain interaction during forward growth and can provide a basis for useful application in nanodomain engineering and development of non-linear optical frequency converters, data storage, and computing devices

Ferroelectric Domain Structure and Local Piezoelectric Properties of Lead-Free (Ka(0.5)Na(0.5))NbO3 and BiFeO3-Based Piezoelectric Ceramics

Recent advances in the development of novel methods for the local characterization of ferroelectric domains open up new opportunities not only to image, but also to control and to create desired domain configurations (domain engineering). The morphotropic and polymorphic phase boundaries that are frequently used to increase the electromechanical and dielectric performance of ferroelectric ceramics have a tremendous effect on the domain structure, which can serve as a signature of complex polarization states and link local and macroscopic piezoelectric and dielectric responses. This is especially important for the study of lead-free ferroelectric ceramics, which is currently replacing traditional lead-containing materials, and great efforts are devoted to increasing their performance to match that of lead zirconate titanate (PZT). In this work, we provide a short overview of the recent progress in the imaging of domain structure in two major families of ceramic lead-free systems based on BiFeO3 (BFO) and (Ka0.5Na0.5)NbO3 (KNN). This can be used as a guideline for the understanding of domain processes in lead-free piezoelectric ceramics and provide further insight into the mechanisms of structure–property relationship in these technologically important material families

Local Study of Lithiation and Degradation Paths in LiMn2O4 Battery Cathodes: Confocal Raman Microscopy Approach

Lithium manganese-based cathodes are widely used in rechargeable batteries due to their low cost, safety, and ecological stability. On the other hand, fast capacity fade occurs in LiMn2O4 mainly because of the induced manganese dissolution and formation of additional phases. Confocal Raman microscopy provides many opportunities for sensitive and spatially resolved structural studies of micro- and nanoscale phenomena. Here, we demonstrate advantages of confocal Raman spectroscopy approach for uncovering the mechanisms of lithiation/delithiation and degradation in LiMn2O4 commercial cathodes. The analysis of Raman spectra for inspecting local lithiation state and phase composition is proposed and exploited for the visualization of the inhomogeneous distribution of lithium ions. The cycling of cathodes is shown to be followed by the formation and dissolution of the Mn3O4 phase and local disturbance of the lithiation state. These processes are believed to be responsible for the capacity fade in the commercial batteries

Temperature Effect on the Stability of the Polarized State Created by Local Electric Fields in Strontium Barium Niobate Single Crystals

The stability of ferroelectric domain patterns at the nanoscale has been a topic of much interest for many years. We investigated the relaxation of the polarized state created by application of a local electric field using a conductive tip of a scanning probe microscope for the model uniaxial relaxor system SrxBa1−xNb2O6 (SBN) in its pure and Ce-doped form. The temporal relaxation of the induced PFM contrast was measured at various temperatures. The average value of the induced contrast decreases during heating for all investigated crystals. Below the freezing temperature the induced state remains stable after an initial relaxation. Above the freezing temperature the induced state is unstable and gradually decays with time. The stability of the induced state is strongly affected by the measuring conditions, so continuous scanning results in a faster decay of the poled domain. The obtained effects are attributed to a decrease of the induced polarization and backswitching of the polarized area under the action of the depolarization field

A comparative study of structural and electrical properties in lead-free BCZT ceramics: Influence of the synthesis method

In the present work, various grain size phenomena were studied in promising lead-free piezoelectric ceramics (Ba0.85Ca0.15) (Zr0.10Ti0.90)O3 fabricated via chemical and conventional oxide methods. Phase composition was ascertained by the Rietveld refinement. Average grain size estimated from the microstructure was ∼1.5 μm in the sol-gel derived ceramic (SG-BCZT) which was much smaller than that obtained in coarse grained (∼27 μm) sample prepared by solid state method (SS-BCZT). Systematic investigation of various functional properties viz. dielectric, ferroelectric, piezoelectric and impedance emphasized the profound influence of grain size effects. The increase in grain boundary volume fraction enhanced diffuseness while lowered the dielectric peak in SG-BCZT. Similarly, increase in elastic stiffness and progressive hindrance to domain wall movements, resulted in a decrease of the remnant polarization and the associated piezoelectric charge coefficient values in small-grained SG-BCZT sample. Accordingly, higher Young's modulus value of 158.3 GPa was observed in SG-BCZT as compared to 117.9 GPa in SS-BCZT. Local-area piezoresponse force microscopy (PFM) images revealed lamellar domains with periodicity 250 ± 90 nm in SS-BCZT while small sized fractal-like irregular domains with an estimated domain width of 150 ± 60 nm were registered in SG-BCZT. Complex impedance spectroscopy results along with grain boundary conductivity were also guided by grain size effect. The mechanisms of grain size driven effects and their impact on the functional properties were discussed.publishe

Exploring Charged Defects in Ferroelectrics by the Switching Spectroscopy Piezoresponse Force Microscopy

Monitoring the charged defect concentration at the nanoscale is of critical importance for both the fundamental science and applications of ferroelectrics. However, up-to-date, high-resolution study methods for the investigation of structural defects, such as transmission electron microscopy, X-ray tomography, etc., are expensive and demand complicated sample preparation. With an example of the lanthanum-doped bismuth ferrite ceramics, a novel method is proposed based on the switching spectroscopy piezoresponse force microscopy (SSPFM) that allows probing the electric potential from buried subsurface charged defects in the ferroelectric materials with a nanometer-scale spatial resolution. When compared with the composition-sensitive methods, such as neutron diffraction, X-ray photoelectron spectroscopy, and local time-of-flight secondary ion mass spectrometry, the SSPFM sensitivity to the variation of the electric potential from the charged defects is shown to be equivalent to less than 0.3 at% of the defect concentration. Additionally, the possibility to locally evaluate dynamics of the polarization screening caused by the charged defects is demonstrated, which is of significant interest for further understanding defect-mediated processes in ferroelectrics.publishe

Correlative Confocal Raman and Scanning Probe Microscopy in the Ionically Active Particles of LiMn2O4 Cathodes

In this contribution, a correlative confocal Raman and scanning probe microscopy approach was implemented to find a relation between the composition, lithiation state, and functional electrochemical response in individual micro-scale particles of a LiMn2O4 spinel in a commercial Li battery cathode. Electrochemical strain microscopy (ESM) was implemented both at a low-frequency (3.5 kHz) and in a high-frequency range of excitation (above 400 kHz). It was shown that the high-frequency ESM has a significant cross-talk with topography due to a tip-sample electrostatic interaction, while the low-frequency ESM yields a response correlated with distributions of Li ions and electrochemically inactive phases revealed by the confocal Raman microscopy. Parasitic contributions into the electromechanical response from the local Joule heating and flexoelectric effect were considered as well and found to be negligible. It was concluded that the low-frequency ESM response directly corresponds to the confocal Raman microscopy data. The analysis implemented in this work is an important step towards the quantitative measurement of diffusion coefficients and ion concentration via strain-based scanning probe microscopy methods in a wide range of ionically active materials

Revealing Lithiation Kinetics and Battery Degradation Pathway in LiMn₂O₄-Based Commercial Cathodes via Electrochemical Strain Microscopy

The capacity fade during the cycling of lithium batteries is a key factor limiting further progress in the improvement of electric vehicles, wearable electronic devices, alternative energy sources, etc. One of the main reasons for capacity loss is battery cathode degradation, which significantly influences the battery lifetime. Despite in-depth knowledge of battery degradation at the chemical level, the kinetics of the degradation at the resolution of the individual elements of the cathode are not fully understood. Here, we studied lithiation kinetics in commercial cathodes based on lithium manganese spinel using the electrochemical strain microscopy local method. Supported by the experimental finding, the “viscous fingers” model of lithium ions intercalation–deintercalation in individual particles of the cathode was proposed. The non-linear dynamics of the lithiation front were suggested to be stimulated by the non-uniform stress field and gradient of the chemical potential. Irregularity of the lithiation front causes the formation of the residual lithiated pocket in the delithiated particles, which effectively reduces the volume available for chemical reaction. The obtained results shed further light on the degradation of the lithium battery cathodes and can be applicable for other cathode materials

Competition between Ferroelectric and Ferroelastic Domain Wall Dynamics during Local Switching in Rhombohedral PMN-PT Single Crystals

The possibility to control the charge, type, and density of domain walls allows properties of ferroelectric materials to be selectively enhanced or reduced. In ferroelectric–ferroelastic materials, two types of domain walls are possible: pure ferroelectric and ferroelastic–ferroelectric. In this paper, we demonstrated a strategy to control the selective ferroelectric or ferroelastic domain wall formation in the (111) single-domain rhombohedral PMN-PT single crystals at the nanoscale by varying the relative humidity level in a scanning probe microscopy chamber. The solution of the corresponding coupled electro-mechanical boundary problem allows explaining observed competition between ferroelastic and ferroelectric domain growth. The reduction in the ferroelastic domain density during local switching at elevated humidity has been attributed to changes in the electric field spatial distribution and screening effectiveness. The established mechanism is important because it reveals a kinetic nature of the final domain patterns in multiaxial materials and thus provides a general pathway to create desirable domain structure in ferroelectric materials for applications in piezoelectric and optical devices