Multitudinous topological configurations spawn new oases of novel phenomena and physical properties in condensed-matter physics1. Nano-sized ferroelectric bubble domains with various polar topologies (e.g., vortices, skyrmions) achieved in ferroelectric films present great potential for valuable physical properties2–5. However, experimentally manipulating bubble domains has remained elusive especially in the bulk form. Here, for the first time in any bulk material, we achieve self-confined bubble domains with multiple polar topologies in bulk Bi0.5Na0.5TiO3 ferroelectrics, especially skyrmions, as validated by direct Z-contrast imaging. This phenomenon is driven by the interplay of bulk, elastic and electrostatic energies of coexisting modulated phases with strong and weak spontaneous polarizations. We demonstrate reversable and tip-voltage magnitude/time-dependent donut-like domain morphology evolution towards continuously and reversibly modulated high-density nonvolatile ferroelectric memories.
Physical Sciences - Article
Nanoscale bubble domains with polar topologies in bulk ferroelectrics
https://doi.org/10.21203/rs.3.rs-115081/v1
This work is licensed under a CC BY 4.0 License
Journal Publication
published 15 Jun, 2021
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nanoscale bubble domains
polar topologies
bulk ferroelectrics
For ferroic materials, spatial variations in the orientation of order parameters (strain, polarization and magnetization) are accommodated through the formation of discrete domains6. Separated by domain walls, normally, different orientations of ordering vectors are expected in adjacent different domains, while they are constant within the same domain6. However, this conventional notion of ferroic domain microstructure is not the only way in which ordering vectors can be arranged spatially6-10. Nano-sized ferroelectric bubble domains, presenting polar topologies (e.g., vortices, skyrmions), were recently achieved in thin film superlattices of (PbTiO3)n/(SrTiO3)n2-5. However, such novel domain structures have not so far been achieved in a bulk material. If it were possible to stabilize these structures, we could achieve multi-conformational domain structures with new physical properties, e.g., chirality, ultrahigh memory density (exceeding tens of Tb in−2), low power consumption, and colossal electromechanical activity2-5,11,12, in economical bulk materials for practical applications. In ferromagnetic materials, the Dzyaloshinskii-Moriya interaction (DMI) can be used as the driving force for stabilizing and eventually manipulating these bubble domains, but is not available in ferroelectrics. To trigger the continuous rotation of electrical dipoles in ferroelectric materials, alternative driving forces must be found, which has been a major endeavor in recent years. Thin films allow better control over the ferroelectricity and depolarization field, and by varying the epitaxial constraint between the ferroelectric and paraelectric layers, polar bubble domains with various polar topologies have been observed in high-quality multilayer thin films3-5. Nevertheless, no such effective epitaxial constraint is applicable to bulk materials, which narrows the experimental options for triggering and further utilizing these topological configurations in bulk ferroelectrics.
Theoretical and experimental findings suggest that kinetic constraint possibly exists in systems that exhibit two or more distinct modulated phases, and therefore should also apply to bulk materials13. Relaxor ferroelectrics, with decoupled dipoles (of multiple symmetries) naturally coexisting in local regions14, may just satisfy the requirement of this kinetic constraint. In their free energy expansion, the high-order gradient terms could provide a negative wall energy, which could drive modulations of polarization vectors as well as domain configurations13. Regulated by this constraint, labyrinthine and stripe domain structures can be achieved in thin-film or bulk relaxor ferroelectrics13,15-17, but not yet for bubble domains. etermined by a critical balance among elastic, electrostatic and gradient energy terms, bubble domains might be stable only within a very narrow range of boundary conditions. It leads to the longstanding challenge of capturing such special domain structure in relaxor ferroelectrics2-5,17, especially for bulk ferroelectrics that lack the epitaxial constraint of multi-layer thin films.
Bi0.5Na0.5TiO3-based relaxor ferroelectrics possess concomitantly modulated short-range-ordered crystal symmetries (mainly R3c and P4bm), based on which, we have manipulated the domain conformations through modifying the local structural heterogeneity. Labyrinthine, stripe, bubble and even polar-skyrmion domains are demonstrated using a combination of Z-contrast imaging and phase-field modelling. For the first time, we experimentally validate the possibility of triggering the bubble domains in bulk ferroelectrics, achieving multiple polar topologies, especially polar skyrmions. The total free energy of bulk ferroelectrics is mainly affected by the competition of bulk, elastic and electrostatic energy terms of coexisting modulated phases, which determines the observed bubble domains, especially for vortices or skyrmions. Not only do we demonstrate the possibility of triggering the bubble domains in bulk ferroelectrics, but also our results demonstrate that Bi0.5Na0.5TiO3-based relaxor ferroelectrics represent a completely new material family exhibiting polar skymions. It opens up a new direction to understand the puzzles on topologies (e.g, skymions) and design new functionalities previously inaccessible in bulk materials. Here, we propose one possibility, manipulating the reversable and tip-voltage magnitude/time-dependent donut-like domain morphologies, which holds potential for designing high-density nonvolatile ferroelectric memories that can be continuously and reversibly modulated. In addition to the prerequisite requirement for applications, reversibility, the ability for continuous modulation holds promise for creating a series of memory states, superior to the conventional “0” and “1” states.
Using piezo-force microscopy (PFM), the composition-induced domain evolution is demonstrated by the induced phase change (Fig. 1a), which ties in closely with the transition from the nonergodic relaxor (NR) state to the ergodic relaxor (ER) state18,19. For easy description, we abbreviate the chemical formulas for different compositions, and the details are provided in the Methods section. By doping appropriate elements, the domain pattern can be regulated from large-size labyrinthine domains [BNT, NR state], to refined stripe domains [BNKT, metastable state (Meta) 1, consisting of NR and ER states where NR plays the dominant role), then to ultrafine stripe domains (BNKLSTT, Meta 2, consisting of NR and ER states where ER plays the dominant role) and finally to bubble domains (BNKLSTT-higher Sr, ER state). Moreover, these bubble domains can be transformed back to the large-sized labyrinthine domains through the opposite path, as PbTiO3 is further introduced into the bubble composition. Notably, during this domain transition process, we also observe a reversible trend in electrical properties accordingly (Extended Data Fig. 2).
Having the obvious morphology evolution of labyrinthine, ultrafine stripe and bubble domains from a macroscopic level, their local polarization states turn out to be critical to reveal the structural details of the chemically driven domain evolution. For ferroelectric materials, their local structures are determined by local polarizations. For Bi0.5Na0.5TiO3-based materials, the displacement of the center Ti4+ cation with respect to the corner Bi3+/Na+ cations (δTi-Bi/Na) or the center of its nearest O2- neighbors (δTi-O) can be used to represent the local polarization state (Extended Data Fig. 1c). To directly see the local atom displacement, aberration-corrected scanning transmission electron microscopy (STEM) was employed due to its ultrahigh resolution and Z-contrast feature for direct atom identification (Extended Data Fig. 1c). Furthermore, the large probe-forming aperture available on our system allows a depth of field of around 5 nm, assisting us to image a thin section through the 3D domain structure.
For a better view, the polarization vectors are overlaid on their corresponding intensity 
, which clearly show the local structure transition from large-sized labyrinthine (Fig. 1b) to refined stripe (Fig. 1c) and then to bubble (Fig. 1d) domains. In analogy to the domain wall of traditional ferroelectric domains, a domain wall width of about 1-2 unit cells can still be observed for the stripe domains (Fig. 1c) while the domain wall is curved and broadened for bubble domains (Fig. 1d).
Polarization vectors of bubble domain boundaries present a continuous rotation, in complete contrast to those of the well-defined traditional ferroelectric domains2. Consistent with the observations by PFM, low magnitude TEM bright-field images of representative BNT-bubble samples present arrays of self-confined circular domains (inset of Extended Data Fig. 4). Statistical analysis of domain width distribution (Extended Data Fig. 4) obtained from PFM and low magnitude TEM images indicates that the average size of the bubble domains is around 25 nm. The combined PFM and TEM images demonstrate that the chemically driven domain morphology evolution and the observed self-confined bubble-like feature clearly differentiate Bi0.5Na0.5TiO3-based materials from their peers.
The polarization vectors of bubble domains show several representative conformational topologies, e.g., arranging along one particular direction and rotating continuously among different directions. Most significantly, we find continuous electric dipole rotation showing flux-closure Bloch-like-skyrmion topologies (Fig. 2a and Extended Data Fig. 5a and 5b), which have never been reported in any bulk material. Moreover, in some areas, the polarization vectors converge from the edge to the center (Fig. 2b and Extended Data Fig. 5c), exhibiting the form of a converging hedgehog-like skyrmion structure4. Polarization vectors also propagate away from a disclination point (Fig. 2c and Extended Data Fig. 5d), showing the form of a diverging hedgehog-like skyrmion structure5. These observations of bubble domains point to the formation of polar-skyrmion structures with both a Bloch-like component, where the polarization vectors rotate smoothly in a flux-closure form (Fig. 2a and Extended Data Fig. 5a and 5b), as well as two hedgehog-like Néel components, where the polarization vectors rotate smoothly from the center to the edge or vice versa (Fig. 2b, 2c and Extended Data Fig. 5c, 5d). It is noted that the nanodomains with various polar topologies are much smaller than domains observed in both PFM (Fig. 1a) and low-magnification TEM (Extended Data Fig. 4). The wenny domains with fuzzy boundaries in the larger scale are possibly consisted with finer nanodomains whose polarizations have certain preference direction in average. Such hierarchical domain pattern would be highly sensitive to the applied electric field, which actually involves more complex and synergistic movements among the nanodomains with multiple polar topologies.
The observed polarization behaviors raise fundamental questions on their physical origin. According to phenomenological theory, relaxor ferroelectrics with coexisting symmetries have higher-order gradient terms in their free energy expansion13,20-24, compared to those with a single symmetry, which could further flatten the free-energy landscape and naturally give rise to polarization modulation (Fig. 2d). Slightly deviated from the parent perovskite cubic symmetry, short-range ordered crystal symmetries (rhombohedral R3c and tetragonal P4bm, Fig. 3g) of Bi0.5Na0.5TiO3-based materials can be revealed by the presence of superlattice ½{ooo}-type and ½{ooe}-type (o and e stand for odd and even Miller indices) reflections, respectively21,22. Selected area electron diffraction (SAED) patterns along three basic zone axes ([001]pc, [110]pc, [111]pc) reveal the increased intensity of ½{ooe}-type reflections with a decreased intensity of ½{ooe}-type reflections from BNT-labyrinthine to BNT-stripe and then to BNT-bubble samples, as shown in Fig. 3(b1-b3) and 3(d1-d3). More precisely, peak intensity ratios of ½{110} over {110} and ½{111} over {111} are obtained (Fig. 3e) through intensity profiles whose width covers both main spots and the reflection sports. The enhanced or lowered intensity of ½{ooe}-type or ½{ooo}-type diffraction spots indicates the increasing ratio of the shorter-range-correlated P4bm symmetry, which is consistent with the high-resolution X-ray diffraction Rietveld refinement analysis (Fig. 3f and Extended Data Fig. 6). Due to the antiparallel displacement between A-site and B-site ions with respect to the oxygen octahedron, P4bm symmetry exhibits ferrielectric features and has a weak spontaneous polarization23,24, while R3c symmetry shows ferroelectric features with a strong polarization22-24. To minimize the polarization discontinuity, the interfacial energies (including electrostatic, elastic and gradient energies) favor the polarization modulation between the coexisting symmetries. Therefore, P4bm symmetry plays a crucial role in restraining the domain boundary, as the depolarization field does, while R3c determines the main body of the bubble domains. The increasing ratio of P4bm is expected to segment the large-sized domains. If R3c/P4bm symmetries coexist in a critical ratio range, bubble domains or even polar skyrmions can be realized in Bi0.5Na0.5TiO3-based bulk ferroelectrics. As revealed by the macro and local structural analysis, the domain morphology evolution is tightly correlated with the ferroelectric- ferrielectric symmetry transition.
Below, we combine phase-field modeling and theoretical rationalization to reveal the physical origin of the above-mentioned observations, including (1) composition-induced domain evolution; (2) microscopic features of the bubble domains; and (3) the skyrmion-like topological conformations.
With phase-field modeling, we reproduce the composition-regulated evolution of domain patterns, from the large-sized labyrinthine-like domains to the refined stripe-like domains and finally to the distinctive bubble-like domains with polar topologies (upper part of Fig. 4a and Extended Data Fig. 7). Consistent with the continuously distributed two-dimensional (2D) polarizations of bubble-domains (Fig. 2a to 2c), the three-dimensional (3D) polarization of a highly doped system also exhibits a similar continuous distribution (bottom part of Fig. 4a). The expanded region derived from a slice of the bubble-like domains shows a clear vortex structure, as shown in the upper-right corner of Fig. 4a.
The origin of the bubble domains is explored based on time-dependent Ginzburg-Landau simulations. Generally, the total free energy of bulk ferroelectrics can be decomposed into bulk, gradient, elastic and electrostatic energies25-27, and the competition of these energy terms determines the most stable domain configuration. Briefly, we consider a prototypical ferroelectric material with multiple symmetries described by a polarization field and then introduce the doping-induced defects as built-in random fields of various magnitudes. By considering and comparing several factors (background dielectric permittivity, doping concentration, doping intensity, doping range and anisotropy factor) that determine the energy terms, it is found that the doping concentration c greatly influences the number of vortices and the background dielectric permittivity εbr (Fig. 4b and Extended Data Fig. 8-11) is the second influence factor. Due to the strong strain–polarization coupling in ferroelectrics, the local stress field induced by doping plays an important role in adjusting the ratio of IP (in-plane) and OP (out-of-plane) polarizations. The electrostatic interactions favor the IP dipole orientation, which rationalizes the fact that a larger εbr for Bi0.5Na0.5TiO3-based solid solutions is helpful to regulate the domain conformations. These combined factors substantially influence the formation of polar bubble domains and even vortices or skyrmions.
The main driving forces to regulate the domain conformations lie in the interplay of the bulk, elastic and electrostatic energies of coexisting modulated phases. Based on the phase-field modeling results for bubble domains, the typical case, polar skyrmions, is presented here. Fig. 4c displays a 3D representation showing the polar skyrmion-like topological conformations. The distributions of IP and OP polarizations are clearly revealed from this 3D perspective. The up and down OP polarizations are smoothly connected by IP polarizations. Consistent with the experimental observations (Fig. 2b and 2c), polar regions with diverging and converging polarizations (Néel form) are observed at the top and bottom of the skyrmion, respectively. In the middle of the skyrmion, IP polarizations rotate continuously (Bloch form), smoothly bridging the up and down OP polarizations. The combined experimental and theoretical results demonstrate the existence of bubble domains and even polar skyrmions in bulk Bi0.5Na0.5TiO3-based solid solutions. Such peculiar 3D topological structure differentiates from the ordinary 2D skyrmions observed in magnetic systems28. Moreover, the polar skyrmion structure seen here is a particular case of the various bubble domains observed in the present bulk system. In addition to the 2D flux-closure vortices (regions Ⅰ-Ⅳ in Fig. 4d) and 3D flux-closure skyrmions (Fig. 4c), the polarization vectors also rotate in non-flux-closure form (region Ⅴ in Fig. 4d and Extended Data Fig. 12). Collectively, these topological conformations constitute the bubble domains with multiple polar topologies observed in bulk Bi0.5Na0.5TiO3-based solid solutions, as demonstrated by both experimental (Fig. 1-3) and theoretical (Fig. 4) observations.
Bubble domains, often seen as the initial state of the ferroelectric domain switching process, are kinetically unstable and difficult to be captured2-5. The bubble domains are stable only within a narrow range of boundary conditions determined by a balance among elastic, electrostatic and gradient energy terms. In this case, the bubble domain state would be easily affected by external forces (chemical pressure, mechanical pressure, voltage, etc.) 2-5,8. Due to the E-field-induced polarization rotation from the IP to OP directions, such metastable and short-range correlated bubble-like topological patterns are expected to experience an E-field-induced conformational transition, leading to the enhanced piezoelectric responses during the voltage loading process3,8. To test the local piezoelectric response and conformational transition during the polarization rotation process, switching spectroscopic PFM (SSPFM) hysteresis behavior was investigated on the bubble domains (Extended Data Fig. 14g). In the first hysteresis cycle, the amplitude signal increases steeply from 0 to –20 V, which signifies that the bubble domains are undergoing the polarization rotation process and could give large piezoelectric responses. Phase images inset in Extended Data Fig. 14g were derived from local regions before and after PFM hysteresis loop measurement, which demonstrate the transformation from bubble to cylindrical domain states. It is worth mentioning that the bubble domains surrounding the formed cylindrical domain, far away from the voltage tip, can coalesce into the large-sized anti-phase domains, see the reverse contrast of the phase image (Extended Data Fig. 14h, 14i). Such stable alternating current (A.C.) voltage-induced antiphase domain morphology makes our bubble domains achieved in bulks distinctive in ferroelectrics.3 It would be easier to obtain multifarious domain morphologies by manipulating relative sizes of anti-phase domains in bulk Bi0.5Na0.5TiO3-based ferroelectrics, without injecting large amount of charges through long-time high voltage or under humid conditions29, 30.
In addition to the A.C. voltage utilized in the SSPFM test, a direct current (D.C.) voltage was then applied to the bubble regions to manipulate the domain morphologies. A preprocessing –40 V voltage was first scanned over a 1*1 mm2 bubble region for the initial poling. Then, a unidirectional voltage is applied to one point. Controlling the duration and magnitude of the applied voltage induces peculiar donut-like antiphase domains around this point (Fig. 5, Extended Data Fig. 14, 16). The ferrielectric P4bm symmetry weakens polarizations along the same direction, and its antiparallel polarizations are present to minimize the total free energy, which is notably different from that of the ferroelectric domains in normal bulk ferroelectrics (Extended Data Fig. 17). The magnitude of the tip voltage determines the width of the outer ring, while the application time determines the width of the inner part. Moreover, such tip voltage-induced phase and amplitude contrast of the donut-like domains can be maintained after 72 hours (Extended Data Fig. 16c), indicating good stability of such peculiar voltage-induced self-conformation from the initial bubble domains. More importantly, these tip voltage-manipulated domain morphologies are rewritable. By scanning a large opposite voltage over the same region, the domain morphologies could well return to the initial state.
The observed multifarious peculiar domain morphologies present at least three important features to note, including: (1) continuously varying ferroelectric domain morphologies can be easily manipulated by the duration and magnitude of the applied tip voltage; (2) the donut-like anti-phase domains are spatially stable and experimentally recoverable; (3) two groups of the donut-like domain morphologies induced by opposite tip voltages exhibit mirrored patterns. These results therefore demonstrate the concept of a continuously and reversibly modulated high-density nonvolatile ferroelectric memories, whose operation is linked to the above reversable tip-voltage magnitude/time-dependent domain morphology evolution.
In summary, we report the direct observation of polar bubble domains including polar skyrmions in bulk Bi0.5Na0.5TiO3-based ferroelectrics. This is the first observation of the elusive polar skyrmions, composed of a series of diversely oriented Néel- and Bloch-like conformations, in any bulk ferroic material. The coexisting R3c/P4bm symmetries significantly affect the interfacial energies, and R3c determines the main body of the bubble domains while P4bm restrains the domain boundary. Driven by the interplay of bulk, elastic, and electrostatic energies of coexisting modulated phases, such peculiar topological structures clearly differentiate from the ordinary 2D skyrmions observed in magnetic systems, as well as the 3D skyrmions observed in multilayer thin films. By controlling the duration and magnitude of the applied tip voltage, these polar topologies exhibit donut-like domain morphologies that open up a new concept for potential applications: Beyond reversibility, necessary for the conventional “0” and “1” states, the possibility for novel, non-conventional, high-density nonvolatile ferroelectric memories based on sequential modulation through a series of memory states.
Author contributions
J. W., J. Y. and H. W. conceived the idea of this work. J. Y. fabricated the bulk Bi0.5Na0.5TiO3-based relaxor ferroelectric solid solutions by conventional solid-state-reaction methods. J. Y. and T. H. carried out the PFM measurements. H. W., Y. Z. and S. J. P. performed and analyzed the aberration-corrected STEM experiments. H. Z., H. W., X. T., X. D. and J. S. performed the phase-field simulations. J. Y. performed high resolution-XRD measurements and the Rietveld fitting and electrical measurements. J. W., J. Y., H. W., and S. J. P. analyzed all data and wrote the manuscript with contributions from others. L.-D. Z. and J. Z. provided helpful discussion. All authors discussed the results and commented on the manuscript. H. W. and J. W. guided the projects.
Competing interests
The authors declare no competing interests.
Acknowledgements
This work was supported by the National Science Foundation of China (NSFC No. 51722208, 5197221 and 52061130216). H.W. would like to acknowledge the financial support from Singapore Ministry of Education Tier 1 grant, R-284-000-212-114, for Lee Kuan Yew Postdoctoral Fellowship. S.J.P and H.W. would like to acknowledge the financial support by the Ministry of Education, Singapore under its Tier 2 Grant (Grant No. MOE2017-T2-1-129).
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