Ferroelastic Domain Walls Research Articles

Time and frequency dependent mechanical properties of LaCoO3-based perovskites: Internal friction and negative creep

The internal friction and creep deformation behavior of La0.8Ca0.2CoO3 and pure LaCoO3 mixed ionic electronic conducting perovskite ceramics have been studied by Dynamic Mechanical Analysis and uniaxial compression under constant applied load, respectively. It was found that both the internal friction and creep strain were almost an order of magnitude higher for Ca2+ doped LaCoO3 as compared to pure undoped LaCoO3. The difference in Ca2+ doped LaCoO3 behavior was attributed to the much higher concentration of point defects (e.g., oxygen vacancies) in the structure and their interaction with other mobile defects, such as ferroelastic domain/twin walls, stacking faults, dislocations, etc. Such interactions of numerous point defects with domain walls produce energetic barriers and slow down the movement of ferroelastic domain walls under applied stress. At the same time, the defects' interactions increase the internal friction resulting in a much higher creep strain of La0.8Ca0.2CoO3 as compared to pure LaCoO3, as the creep strain is determined by the distance between the domain wall and its equilibrium position at the onset of the creep process. Therefore, the high friction will result in the larger distance the wall has to move to reach the equilibrium which in turn results in higher creep strain. The expansion of LaCoO3 under constant applied compressive stress, named here as negative creep, was also discovered to occur during room temperature creep experiments.

Dynamic behavior of BiVO4 material under mechanical studies

The mechanical relaxation technique is applied to investigate the fundamental dynamic behavior of BiVO4 material. A prominent internal friction peak is observed around 430 K at 1 Hz, which is actually composed of three sub-peaks (P1, P2 and P3 from low to high temperature). And the associated modulus anomalies can also be found in any of the samples. The peak P1 with activation energy E1 ∼ 3.20 eV is probably related to the stress-induced unequal positions of Bi3+ ions; while the main P2 peak with E2 = 0.91 eV is associated with a complex mechanism, which originates from the viscous motion of domain walls and the interaction of domain walls with oxygen vacancies; and the responsive P3 peak is resulted from the ferroelastic–paraelastic phase transition, accompanied by a minimum modulus value. Based on the relaxation process and crystalline structure of BiVO4, the motion model of ferroelastic domain walls and transport mechanism of diffusion are suggested. Our results pave the way for better understanding the intrinsic dynamic and multifunctional properties of BiVO4.

Linear and nonlinear optical probe of the ferroelectric-like phase transition in a polar metal, LiOsO3

LiOsO3 is one of the first materials identified in the recent literature as a “polar metal,” a class of materials that are simultaneously noncentrosymmetric and metallic. In this work, the linear and nonlinear optical susceptibility of LiOsO3 is studied by means of ellipsometry and optical second harmonic generation (SHG). Strong optical birefringence is observed using spectroscopic ellipsometry. The nonlinear optical susceptibility extracted from SHG polarimetry reveals that the tensor components are of the same magnitude as in the isostructural insulator LiNbO3, except the component along the polar axis d33 is suppressed by an order of magnitude. Temperature-dependent SHG measurements in combination with Raman spectroscopy indicate a continuous order-disorder type polar phase transition at 140 K. Linear and nonlinear optical microscopy measurements reveal 109°/71° ferroelastic domain walls, like in other trigonal ferroelectrics. No 180° polar domain walls are observed to emerge across the phase transition.

Voltage-Controlled Bistable Thermal Conductivity in Suspended Ferroelectric Thin-Film Membranes.

Ferroelastic domain walls in ferroelectric materials possess two properties that are known to affect phonon transport: a change in crystallographic orientation and a lattice strain. Changing populations and spacing of nanoscale-spaced ferroelastic domain walls lead to the manipulation of phonon-scattering rates, enabling the control of thermal conduction at ambient temperatures. In the present work, lead zirconate titanate (PZT) thin-film membrane structures were fabricated to reduce mechanical clamping to the substrate and enable a subsequent increase in the ferroelastic domain wall mobility. Under application of an electric field, the thermal conductivity of PZT increases abruptly at ∼100 kV/cm by ∼13% owing to a reduction in the number of phonon-scattering domain walls in the thermal conduction path. The thermal conductivity modulation is rapid, repeatable, and discrete, resulting in a bistable state or a "digital" modulation scheme. The modulation of thermal conductivity due to changes in domain wall configuration is supported by polarization-field, mechanical stiffness, and in situ microdiffraction experiments. This work opens a path toward a new means to control phonons and phonon-mediated energy in a digital manner at room temperature using only an electric field.

Ferroelastic relaxation at 20 GHz evidenced by large frequency range picosecond acoustics

We present a method to perform elastic measurements on a thin-film as a function of frequency between a few GHz and a few hundred GHz. The technique is mainly based on Picosecond Acoustics (PA), which is an ultrafast optical technique that realizes pulse-echo measurements in the hypersonic range. Here, we combine gold layers serving as transducers and several opto-acoustic detection mechanisms to extend the PA technique to the lowest accessible frequencies (a few GHz) up to hundreds of GHz. We can therefore use the same technique on the same material to explore its elastic properties at a certain frequency over a very large frequency range. We have then applied this technique to explore the elastic properties of a lead zirconate titanate thin film from 3 to 80 GHz. We report a 9% increase in the longitudinal sound velocity above 20 GHz, which corresponds to a 19% increase in the C33 elastic modulus. We interpret such an observation as a direct evidence of ferroelastic domain wall relaxation.

Electric field-induced changes in the ferroelastic behavior of (Na1/2Bi1/2)TiO3-BaTiO3

In this study, the macroscopic mechanical behavior was characterized for poled and unpoled polycrystalline (1−x)(Na1/2Bi1/2)TiO3-xBaTiO3 (NBT-xBT) for compositions across the morphotropic phase boundary (MPB). Due to a field-induced ferroelectric phase transformation, NBT-xBT compositions near the MPB (x = 6–7 mol%) showed a significant decrease in the coercive stress for electrically poled samples. The apparent difference in mechanical behavior is suggested to be due to an irreversible electric-field-induced transformation to long-range ferroelectric order in the poled samples. The results indicate a significant difference in the critical stresses for the relaxor-ferroelectric transition and ferroelastic domain wall motion, which can have important effects on applications for lead-free ferroelectrics. To further illustrate this, a method was developed to electrically depole NBT-xBT at room temperature, resulting in an unpoled NBT-xBT material with long-range ferroelectric order. Mechanical testing revealed analogous macroscopic ferroelastic behavior to the poled samples, despite the lack of a piezoelectric response.

Immobile defects in ferroelastic walls: Wall nucleation at defect sites

Randomly distributed, static defects are enriched in ferroelastic domain walls. The relative concentration of defects in walls, Nd, follows a power law distribution as a function of the total defect concentration C: Nd∼Cα with α=0.4. The enrichment Nd/C ranges from ∼50 times when C = 10 ppm to ∼3 times when C = 1000 ppm. The resulting enrichment is due to nucleation at defect sites as observed in large scale MD simulations. The dynamics of domain nucleation and switching is dependent on the defect concentration. Their energy distribution follows the power law with exponents during yield between ε∼1.82 and 2.0 when the defect concentration increases. The power law exponent is ε≈2.7 in the plastic regime, independent of the defect concentration.

Segmental front line dynamics of randomly pinned ferroelastic domain walls

Dynamic mechanical analysis (DMA) measurements as a function of temperature, frequency, and dynamic force amplitude are used to perform a detailed study of the domain wall motion in LaAlO3. In previous DMA measurements Harrison et al.[Phys. Rev. B69,144101(2004)] found evidence for dynamic phase transitions of ferroelastic domain walls in LaAlO3. In the present work we focus on the creep-to-relaxation region of domain wall motion using two complementary methods. We determine, in addition to dynamic susceptibility data, waiting time distributions of strain jerks during slowly increasing stress. The present dynamic susceptibility data can be well fitted with a power law, where a crossover from stochastic DW motion to the pinned regime is well described using the scaling function of Fedorenko et al.[Phys. Rev. B70, 224104(2004)].

Control of surface potential at polar domain walls in a nonpolar oxide

Ferroic domain walls could play an important role in microelectronics, given their nanometric size and often distinct functional properties. Until now, devices and device concepts were mostly based on mobile domain walls in ferromagnetic and ferroelectric materials. A less explored path is to make use of polar domain walls in nonpolar ferroelastic materials. Indeed, while the polar character of ferroelastic domain walls has been demonstrated, polarization control has been elusive. Here, we report evidence for the electrostatic signature of the domain-wall polarization in nonpolar calcium titanate (CaTiO3). Macroscopic mechanical resonances excited by an ac electric field are observed as a signature of a piezoelectric response caused by polar walls. On the microscopic scale, the polarization in domain walls modifies the local surface potential of the sample. Through imaging of surface potential variations, we show that the potential at the domain wall can be controlled by electron injection. This could enable devices based on nondestructive information readout of surface potential.

Raman signatures of ferroic domain walls captured by principal component analysis

Ferroic domain walls are currently investigated by several state-of-the art techniques in order to get a better understanding of their distinct, functional properties. Here, principal component analysis (PCA) of Raman maps is used to study ferroelectric domain walls (DWs) in LiNbO3 and ferroelastic DWs in NdGaO3. It is shown that PCA allows us to quickly and reliably identify small Raman peak variations at ferroelectric DWs and that the value of a peak shift can be deduced—accurately and without a priori—from a first order Taylor expansion of the spectra. The ability of PCA to separate the contribution of ferroelastic domains and DWs to Raman spectra is emphasized. More generally, our results provide a novel route for the statistical analysis of any property mapped across a DW.

Effect of mechanical depoling on piezoelectric properties of Na0.5Bi0.5TiO3–xBaTiO3 in the morphotropic phase boundary region

The effect of mechanical stress on the direct piezoelectric properties of pre-poled (1 − x)(Na0.5Bi0.5)TiO3–xBaTiO3 (NBT–xBT) in the range 4% ≤ x ≤ 13% was studied in situ using a mechanical load frame. Prior to mechanical loading, compositions near the morphotropic phase boundary (MPB, x = 6–7% BT) exhibited enhanced ferroelectric and piezoelectric properties compared to compositions further from the MPB. Specifically, the lowest ferroelectric coercive field and highest piezoelectric coefficient within this composition range occur at x = 7% BT. During mechanical compression, the MPB compositions exhibited the lowest depoling stress. The results demonstrate that, while favorable piezoelectric and ferroelectric properties can be obtained at compositions near the MPB, these compositions are also the most susceptible to the effects of mechanical depoling. Ferroelastic domain wall motion is suggested as the primary factor that may be responsible for these behaviors.

A-site ordering and its effect on tilting transition in perovskite La0.75Sr0.25FeO3-δ investigated by mechanical spectroscopy

La0.75Sr0.25FeO3-δ polycrystalline samples were prepared by the solid state reaction at different sintering temperatures. An octahedral tilting Pnma↔R3¯c transition in La0.75Sr0.25FeO3-δ was detected by mechanical spectroscopy, where a dip of reduced modulus was observed and accompanied by a sharp internal friction peak. The modulus softening is due to the strain/order parameters coupling at this improper ferroelastic transition. The tilting transition shifts toward lower temperature with reducing sintering temperature in La0.75Sr0.25FeO3-δ samples, which is due to the detriment of A-site ordering in the ABO3 perovskite. A higher degree of A-site ordering favors more homogenous structural modulation, which stabilizes the low temperature Pnma phase and results in the shift of the transition to higher temperature. Another internal friction peak just below the tilting transition was observed, which is attributed to domain wall motions. A correlation between the mobility of ferroelastic domain walls in Pnma perovskite and the existence of the high temperature R3¯c phase was suggested.

Role of flexoelectric coupling in polarization rotations at the a-c domain walls in ferroelectric perovskites

Ferroelectric and ferroelastic domain walls play important roles in ferroelectric properties. However, their couplings with flexoelectricity have been less understood. In this work, we applied phase-field simulation to investigate the flexoelectric coupling with ferroelectric a/c twin structures in lead ziconate titanate thin films. Local stress gradients were found to exist near twin walls that created both lateral and vertical electric fields through the flexoelectric effect, resulting in polarization inclinations from either horizontal or normal orientation, polarization rotation angles deviated from 90°, and consequently highly asymmetric a/c twin walls. By tuning the flexoelectric strengths in a reasonable range from first-principles calculations, we found that the transverse flexoelectric coefficient has a larger influence on the polarization rotation than longitudinal and shear coefficients. As polar rotations that commonly occur at compositional morphotropic phase boundaries contribute to the piezoelectric enhancement, this work calls for further exploration of alternative strain-engineered polar rotations via flexoelectricity in ferroelectric thin films.

Strain intermittency due to avalanches in ferroelastic and porous materials

The avalanche statistics in porous materials and ferroelastic domain wall systems has been studied for slowly increasing compressive uniaxial stress with stress rates between 0.2 and 17 kPa s−1. Velocity peaks are calculated from the measured strain drops and used to determine the corresponding Energy distributions . Power law distributions have been obtained over 4–6 decades. For most of the porous materials and domain wall systems an exponent was obtained in good agreement with mean-field theory of the interface pinning transition. For charcoal, shale and calcareous schist we found significant deviations of the exponents from mean-field values in agreement with recent acoustic emission experiments.

The noise of many needles: Jerky domain wall propagation in PbZrO3 and LaAlO3

Measurements of the sample length of PbZrO3 and LaAlO3 under slowly increasing force (3-30 mN/min) yield a superposition of a continuous decrease interrupted by discontinuous drops. This strain intermittency is induced by the jerky movement of ferroelastic domain walls through avalanches near the depinning threshold. At temperatures close to the domain freezing regime, the distributions of the calculated squared drop velocity maxima N(υm2) follow a power law behaviour with exponents ε=1.6±0.2. This is in good agreement with the energy exponent ε=1.8±0.2 recently found for the movement of a single needle tip in LaAlO3 [R. J. Harrison and E. K. H. Salje, Appl. Phys. Lett. 97, 021907 (2010)]. With increasing temperature, N(υm2) changes from a power law at low temperatures to an exponential law at elevated temperatures, indicating that thermal fluctuations increasingly enable domain wall segments to unpin even when the driving force is smaller than the corresponding barrier.

Thickness-dependent a1/a2 domain evolution in ferroelectric PbTiO3 films

Ferroelectric a1/a2 domain structure has great potentials in high dielectric capacitors and tunable microwave devices. Understanding its structure is crucial to better control the domain configurations for future applications. In this paper, PbTiO3 thin films with variant thicknesses are deposited on (110)-oriented GdScO3 substrates by Pulsed Laser Deposition (PLD) and investigated by using conventional transmission electron microscopy (TEM) and Cs-corrected Scanning TEM. Contrast analysis and electron diffractions reveal that PbTiO3 films are domain oriented consisting of a1/a2 and a/c domain structure. The a1/a2 domains are found to distribute periodically and its width increases with increasing film thickness following square root rule. Cs-corrected STEM imaging demonstrates that the domain walls of a1/a2 domain structure have the rotation characteristic of 90° ferroelastic domain wall. The interchange of a1/a2 domains induces the formation of vertex domains composed of two 90° and one 180° domain walls. Strains are mainly concentrated on the domain walls. The formation of this complex domain configuration is discussed in terms of the effect of the misfit strain, film thickness and cooling rate. These results provide novel information about a1/a2 domain structures and are expected to shed some light on modulating a1/a2 ferroelectric domain patterns in the design of ferroelectric-based devices.

Controlled Charging of Ferroelastic Domain Walls in Oxide Ferroelectrics.

Conductive domain walls (DWs) in ferroic oxides as device elements are a highly attractive research topic because of their robust and agile response to electric field. Charged DWs possessing metallic-type conductivity hold the highest promises in this aspect. However, their intricate creation, low stability, and interference with nonconductive DWs hinder their investigation and the progress toward future applications. Here, we find that conversion of the nominally neutral ferroelastic 90° DWs into partially charged DWs in Pb(Zr0.1Ti0.9)O3 thin films enables easy and robust control over the DW conductivity. By employing transmission electron microscopy, conductive atomic force microscopy and phase-field simulation, our study reveals that charging of the ferroelastic DWs is controlled by mutually coupled DW bending, type of doping, polarization orientation and work-function of the adjacent electrodes. Particularly, the doping outweighs other parameters in controlling the DW conductivity. Understanding the interplay of these key parameters not only allows us to control and optimize conductivity of such ferroelastic DWs in the oxide ferroelectrics but also paves the way for utilization of DW-based nanoelectronic devices in the future.

Bulk and domain-wall effects in ferroelectric photovoltaics

We investigate the photovoltaic (PV) effects in ferroelectrics based on the polar structure in domains and the intrinsic symmetry breaking of ferroelastic domain walls (DWs). A comprehensive analysis for $\mathrm{BiFe}{\mathrm{O}}_{3}$ films with the single-domain and 71\ifmmode^\circ\else\textdegree\fi{} domain structures reveals a major contribution of the DWs superimposed on the bulk PV effect, which can explain the enhanced PV response in the multidomain film exhibiting photovoltages greater than the band gap. Our methodology can reveal the contributions of the bulk PV and the DW-PV effects quantitatively and uncover a design strategy for enhancing ferroelectric photovoltaics.

Nanoscale Origins of Ferroelastic Domain Wall Mobility in Ferroelectric Multilayers.

The nanoscale origins of ferroelastic domain wall motion in ferroelectric multilayer thin films that lead to giant electromechanical responses are investigated. We present direct evidence for complex underpinning factors that result in ferroelastic domain wall mobility using a combination of atomic-level aberration corrected scanning transmission electron microscopy and phase-field simulations in model epitaxial (001) tetragonal (T) PbZrxTi1-xO3 (PZT)/rhombohedral (R) PbZrxTi1-xO3 (PZT) bilayer heterostructures. The local electric dipole distribution is imaged on an atomic scale for a ferroelastic domain wall that nucleates in the R-layer and cuts through the composition breaking the T/R interface. Our studies reveal a highly complex polarization rotation domain structure that is nearly on the knife-edge at the vicinity of this wall. Induced phases, namely tetragonal-like and rhombohedral-like monoclinic were observed close to the interface, and exotic domain arrangements, such as a half-4-fold closure structure, are observed. Phase field simulations show this is due to the minimization of the excessive elastic and electrostatic energies driven by the enormous strain gradient present at the location of the ferroelastic domain walls. Thus, in response to an applied stimulus, such as an electric field, any polarization reorientation must minimize the elastic and electrostatic discontinuities due to this strain gradient, which would induce a dramatic rearrangement of the domain structure. This insight into the origins of ferroelastic domain wall motion will allow researchers to better "craft" such multilayered ferroelectric systems with precisely tailored domain wall functionality and enhanced sensitivity, which can be exploited for the next generation of integrated piezoelectric technologies.

Domain imaging in ferroelectric thin films via channeling-contrast backscattered electron microscopy

Ferroelastic domain walls provide opportunities for deterministically controlling mechanical, optical, electrical, and thermal energy. Domain wall characterization in micro- and nanoscale systems, where their spacing may be of the order of 100 nm or less is presently limited to only a few techniques, such as piezoresponse force microscopy and transmission electron microscopy. These respective techniques cannot, however, independently characterize domain polarization orientation and domain wall motion in technologically relevant capacitor structures or in a non-destructive manner, thus presenting a limitation of their utility. In this work, we show how backscatter scanning electron microscopy utilizing channeling contrast yield can image the ferroelastic domain structure of ferroelectric films with domain wall spacing as narrow as 10 nm. Combined with electron backscatter diffraction to identify grain orientations, this technique provides information on domain orientation and domain wall type that cannot be readily measured using conventional non-destructive methods. In addition to grain orientation identification, this technique enables dynamic domain structure changes to be observed in functioning capacitors utilizing electrodes that are transparent to the high-energy backscattered electrons. This non-destructive, high-resolution domain imaging technique is applicable to a wide variety of ferroelectric thin films and a multitude of material systems where nanometer-scale crystallographic twin characterization is required.