Materials Research Bulletin 131 (2020) 110981

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Materials Research Bulletin

journal homepage: www.elsevier.com/locate/matresbu

Deterministic control of toroidal moment in ferroelectric nanostructures by T

direct electrical field
Do Van Truonga,b,*, Ngoc Giang Trana, Vuong Van Thanhc, Tran The Quanga
a
Department of Mechatronics, Hanoi University of Science and Technology, Ha Noi, Viet Nam
b
International Research Center for Computational Materials Science, Hanoi University of Science and Technology, Ha Noi, Viet Nam
c
Department of Design of Machinery and Robot, Hanoi University of Science and Technology, Ha Noi, Viet Nam

A R T I C LE I N FO A B S T R A C T

Keywords: A deterministic control of vortex chirality in ferroelectrics under a direct electric field is a challenging task. In
Ferroelectric nanostructure this study, a novel method is proposed to deterministically switch a single polarization vortex in either a fer-
Single polarization vortex roelectric nanowire or a ferroelectric nanodot by using asymmetry electric field. Based on atomic simulations in
PbTiO3 nanowire the framework of the shell model, we demonstrate that the single polarization vortex is easily formed in fer-
PbTiO3 nanodot
roelectric nanowire or nanodot from a pair of 180°domains, which is generated by asymmetry electric field.
More importantly, the use of asymmetry electric field can switch the direction of the 180° domains, and thereby,
deterministically switch the chirality of polarization vortex. The present study provides instructive guideline for
the future development of nanoscale ferroelectric devices in general and of FRAM in particular.

1. Introduction ferroelectric systems with rational designs of nanostructures, such as

asymmetric ferroelectric nanorings [21], dot-film system [22], and
Nanoscale ferroelectrics have recently been vigorously studied fol- asymmetric ferroelectric nanodisks [23]. Another attempt has been
lowing the exploration of unusual polarization domain structures such made to switch the vortex chirality by homogenous electric field with
as polarization vortices [1], which have rapidly emerged as a potential the mediation of asymmetric mechanical fields caused by substrate,
candidate for advanced or even novel applications in FRAM [2,3], dislocations, and local clamping force [24]. The proposed methods for a
sensors, actuators, transducers [4,5], transistors [6], solar cells [7], and vortex switching by homogeneous electric field, however, require a
switchable photovoltaics [8]. The vortex structures were first suggested sophisticated design and fabrication of ferroelectric nanostructures. In
by Kittel for ferromagnetic systems [9], and then translated into fer- addition, although it is possible to realize single-vortex switching by a
roelectric systems [1]. In thin (or even ultrathin) film structures, several homogeneous electric, the switching process of polarization vortex
investigations on the ferroelectric critical size have revealed that before often displays complex spatio-temporal features, where the vortex is
the thin film reaches its critical size, the common stripe domains are catastrophically altered with a transformation through a far mediated
rearranged into the closure quadrant domains or polarization vortices state such as single vortex, before it reaches to the reversed state. This
[10–13], yielding zero net polarization. The formation of polarization gives rise to an overriding concern about a deterministic switching of
vortices has been demonstrated to depend on several factors such as the polarization vortex chirality. Therefore, a deterministic switching of
terminated surfaces [14–16], the thickness [10] and the boundary vortex chirality in ferroelectric nanostructures remains challenging.
conditions (electrical and mechanical boundary conditions) [17] of thin In this study, we use atomic simulations in the framework of the
film. On the other hand, not only the formation of vortices, but also a shell model to find out a base to form a single polarization vortex in
deterministic switching of vortex chirality is of importance for a reliable ferroelectric nanostructures including nanowire and nanodot, based on
implementation of vortices in advanced applications. Therefore, nu- the polarization vortices experimentally observed in ferroelectric thin
merous attempts have been made to switch the vortex chirality. An films [12,13]. More importantly, we propose a deceptively simple yet
early idea is the use of a curled electric field to switch the vortex incisive method that can deterministically switch the single polariza-
chirality [18–20]. However, the required magnitude of applied field for tion vortex by a direct electric field.
the switching is practically difficult to generate. Recently, homo-
geneous electric field has been suggested to switch vortex chirality in

⁎
Corresponding author at: Department of Mechatronics, Hanoi University of Science and Technology, Ha Noi, Viet Nam.
E-mail address: [email protected] (D. Van Truong).

https://doi.org/10.1016/j.materresbull.2020.110981
Received 12 November 2019; Received in revised form 18 May 2020; Accepted 28 June 2020
Available online 06 July 2020
0025-5408/ © 2020 Elsevier Ltd. All rights reserved.
D. Van Truong, et al. Materials Research Bulletin 131 (2020) 110981

2. Calculation method – core shell model Table 2

Parameters of potential functions in shell model for PbTiO3.
Theoretically, ab initio calculations based on the density functional Species X (e) Y (e) k2 (eV Å−2) k4 (eV Å−4)
theory [25,26] have been commonly used in researches on ferroelectric
materials to provide the origin of phenomena observed in ferroelectric Pb +5.49586 −3.63322 129.408999 41861.509708
Ti +19.36901 −16.27952 8428.836044 99652150.211023
materials and predict unusual physico-mechanical properties. In spite
O +2.54843 −4.19917 179.379501 −3560.826943
of their powerful approach, the ab initio calculations require heavy Interactions A (eV) C (eV Å6) ρ (Å)
computation and are usually limited to a few hundred atoms in the Pb–O 2501.105048 0.231585 0.306122
simulation system. This makes it critically difficult for further in- O–O 1139.341138 72.673182 0.266229
vestigations on ferroelectrics approaching real-size nanostructures. Al- Ti–O 2559.834378 5.350582 0.282161
Pb–Ti 464.653659 206.772977 0.398264
ternatively, atomic simulation using the interatomic potentials on the
basic of the shell model [27–29] is more efficient and is selected to
simulate the PbTiO3 thin film, nanowire and nanodot in this study. The nanowires, and nanodots. The local polarization vector P is finally
potential functions, which are the key of the shell model, are evaluated calculated based on the atom positions after relaxing the structure, as
by fitting the obtained results for the elastic constants and the lattice [28,29,31]
constants of tetragonal PbTiO3 bulk to that derived from ab initio cal-
e N
culations. In the shell model, each atom assumed consists of two P= ∑ wm Zm* um
Ω m=1 (4)
charged particles, a positive core X and a negative shell Y. The sum of
charges is equal to the total ionic charge. The electrical polarization where e, Ω and um denote the electron charge, the volume of unit cell,
occurred is due to the displacement between the shell and the core. and the displacement of atom m from its ideal lattice, respectively. Zm*
Three kinds of potential function as the long-range VLR, the short-range are the Born effective charge tensors calculated by Zhong et al. [32].
VSR, and the core-shell spring VCS potentials are used in the shell model, The weight factors wm are set to 1 for Pb, 1/8 for Ti, and 1/4 for O,
which are defined as which correspond to the number of unit cells sharing the atom. These
qi qj 1 values have been validated and used in previous studies [11,33]. In the
VLR = present study, the TiO2-centered plane is selected as a symmetric one to
4πεo rij (1)
evaluate the local polarization.
To understand deeply the formation of polarization vortices in fer-
r C
VSR = ⎧Aexp ⎜⎛− ⎟⎞ − 6 ⎫ fc roelectric nanostructures, in this study, a free-standing PbTiO3 thin film
⎨
⎩ ⎝ ρ ⎠ r ⎬
⎭ (2) is firstly simulated by using a shell model [27–29] via GULP packet
[30]. The obtained results are compared and verified with experiments
1 2 1
VCS = k2 r + k4 r 4 and ab initio calculations. The simulation model (Fig. 1(a)) composes of
2 24 (3)
14, 2, and 10 unit-cells thick in the x, y, and z directions, respectively.
where rij, qi and εo denote the distance between the ith and jth particles, The lattice constants are of a =3.894 Å and c =4.076 Å (see Table 1).
the charge of core or shell, and the dielectric constant in vacuum, re- The terminated surfaces are TiO2. The periodic boundary conditions are
spectively; fc is the function that limits the distance of interaction applied in the x, y and z directions. To realize the thin film structure,
among ions; and A, ρ, C, k2, and k4 are the parameters of the potential vacuum regions with thickness six times of the lattice constants are
functions. taken into account in the z direction to avoid the undesirable interac-
To calculate the polarization field, the calculation procedure is tion [31]. Since the 180° stripe domain is commonly observed in a thick
performed as follows. Firstly, the lattice constants and elastic constants ferroelectric film, such a domain structure is adopted as an initially
of tetragonal PbTiO3 bulk are determined by ab initio calculations setup for the simulation (Fig. 1(b)).
within the local density approximation as implemented in the Quantum
ESPRESSO code. Then, the parameters of the potential functions as A, ρ, 3. Results and discussions
C, k2, k4 are evaluated by solving a multi-objective optimization pro-
blem that uses Newton-Raphson method implemented in the GULP code The polarization structure in the free-standing thin film after re-
[30] until the sum of squared error of the expecting parameters and the laxing, i.e., at the equilibrium state, is presented in Fig. 1(c). The po-
target parameters between the current and previous steps is less than larization structure with alternative clockwise and counter-clockwise
10−5. Tables 1 and 2 summarize the lattice constants, the elastic con- vortices is formed. More specifically, one vortex at the center and two
stants, and the parameters of the potential functions of tetragonal halves of the vortex at the two sides are formed in the period of the
PbTiO3 bulk obtained from the optimized shell model and ab initio polarization vortex array, and the adjacent vortices have the opposite
calculations. Next, the potential functions with the obtained parameters chiralities (Fig. 1(c)). Noted that an opposite polarization structure can
are used to simulate the PbTiO3 nanostructures including thin films, be obtained by reversing the polarization vectors in the initial 180°
stripe domains. On the other hand, both the simulation and experiment
Table 1 studies have shown that the period of polarization vortex array depends
Lattice constants and elastic constants of PbTiO3 obtained by the shell model on the thickness of thin film [10,12]. For the ultrathin PbTiO3 film, the
and ab initio calculations. ratio of the period/the thickness investigated is approximately 2 [12].
Shell model Ab initio Error The polarization vortex array in Fig. 1(c) achieves a good agreement
with the experimental observation [12]. Furthermore, by ab initio
a (Å) 3.894 3.867 0.69% study, Shimada et al. [11] have revealed that the polarization vortices
c (Å) 4.076 4.034 1.03%
are easily formed from the initial 180° domains. Therefore, the present
c/a 1.047 1.043 0.38%
V (Å3) 61.805 60.323 2.40% study yields consistent results in comparison to that obtained from the
c11 (GPa) 292.050 292.119 0.02% theoretical [11] and the experimental [12,13] studies, which clearly
c12 (GPa) 114.617 114.698 0.07% demonstrates the reliability of the shell model.
c13 (GPa) 90.397 90.451 0.06% In the thin film, there are more than one vortex formed in each
c33 (GPa) 96.717 96.693 0.02%
period of the polarization vortex array [11,12] (Fig. 1(c)), and hence an
c44 (GPa) 58.849 59.163 0.53%
c66 (GPa) 108.347 107.900 0.41% individual switching of each single polarization vortex is challenging.
With desiring to form the single polarization vortex and to control its

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D. Van Truong, et al. Materials Research Bulletin 131 (2020) 110981

Fig. 1. Formation of the polarization vortices in the PbTiO3 thin film. (a) Simulation model for the thin film with the (001) surfaces, the TiO2-terminated surfaces
and the TiO2-centered plane. (b) The initial 180o domain walls are setup in the thin film. (c) The polarization vortices are formed in the equilibrium state.

Fig. 2. Formation of the single polarization vortex in the PbTiO3 nanowire. (a) Simulation model for the thin film with the TiO2- terminated surfaces and the TiO2-
centered plane. (b) The initial 180o domain wall is setup in the nanowire. (c) The single polarization vortex is formed in the equilibrium state.

chirality, a nanowire model is proposed. Fig. 2(a) shows the nanowire domain structures. On the other hand, the size of the polarization
model with 10 unit-cells in height, 14 unit-cells in width (the period of vortex can be altered by changing the cross-section size of the nanodot.
the polarization vortex array) and 2 unit-cells in length. A pair of “up” In the nanowire and nanodot, the formation of single polarization
and “down” domains with a 180° domain wall is adopted as initial vortex is originated from the initial 180° domain structure. In order to
condition for polarization field (Fig. 2(b)). The periodic boundary compose the 180° domain structure in practice, we propose to use an
conditions are applied in all three directions. The thicknesses of the asymmetrical pair of the external electric field (Fig. 3(a)). The process
vacuum regions are set at six times of the lattice constants in the x and z of forming and switching the single polarization vortex by the external
directions. The computational settings are implemented as in the thin electric field can be summarized as follows. The asymmetrical pair of
film model. Remarkably, the result obtained in the nanowire is a single the external electric field is applied on the nanodot (or the nanowire) by
polarization vortex. Fig. 2(c) illustrates the single polarization vortex in electrodes, the polarization vectors are aligned with the direction of the
a representative cell-layer. The polarization vortex core is at the center external applied field. The 180° domain structure is thus established in
of the cell-layer and the shape of the vortex is unchanged layer-by-layer this case (Fig. 3(a)). A gap between the adjacent electrodes is setup, and
along the nanowire length. The formation of single polarization vortex the electrodes are considered as completely insulated. Then, the ex-
is attributed to originate from the physical confinement of the nanowire ternal electric field is removed, the polarization vortex is formed
cross-section and the 180° domain wall initially setup. (Fig. 3(b)). To switch the vortex, we just need to change the sign of the
In a similar manner, a PbTiO3 nanodot model with the size of 14 external electric field pair (Fig. 3(c) and (d)). In Fig. 4, we depict the
unit-cells (in the x direction) × 14 unit-cells (in the y direction) × 10 domain evolution of the nanodot under a rectangular waveform of the
unit-cells (in the z direction) is also obtained the single polarization asymmetrical pair of the external electric field. Several typical points
vortex. Noted that the vortex structure with opposite chirality can be (from A1 to A12) and corresponding polarization domains are selected
achieved by reversing the polarization vectors in the initial 180° to illustrate. A clockwise single vortex state is initially adopted in the

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D. Van Truong, et al. Materials Research Bulletin 131 (2020) 110981

Fig. 3. Formation of the single polarization vortex in the PbTiO3 nanodot by the asymmetrical pair of the external electric field. ((a) and (b)) Storing a data bit 1. (a)
The 180o domain wall is established by applying the asymmetric pair of the external electric field. (b) The single polarization vortex in counterclockwise is formed
after removing the external electric field, and the vortex assigned is the state value 1. ((c) and (d)) Storing a data bit 0. (c) The polarization vectors in the 180o
domain wall are reversed by reversing the sign of the external electric field pair. (d) The single polarization vortex in clockwise is formed after removing the external
electric field, and the vortex assigned is the state value 0.

nanodot, as denoted by the point A1. At the first stage the sign of the asymmetrical pair of the applied electric field.
(A1→A2→A3→A4) of a cycle, the electric field, E, increases but the With the use of single polarization vortex accommodated in nano-
toroidal moment, G [34], decrease. G decreases rapidly from E = 0 to E wire or nanodot for data storage, the physical size of a memory cell can
= 0.85 108 V/m, and then approximates to zero. This reduction is due be significantly decreased in comparison to the use of thin film in the
to the reversal of the polarization vectors under applying the external traditional FRAM. In the same physical size, the number of memory
electric fields E. At the point A4, the polarization vectors are completely cells of FRAM using the ferroelectric nanowire or nanodot can increase
oriented according to the applied electric fields, the vortex core dis- significantly to compare with that using the ferroelectric thin film (the
appears, and G is thus equal to 0. At the second stage size of thin film in the FRAM cell is usually about 2000×2000 × 100
(A4→A5→A6→A7), the external electric fields are removed. G in- nm [2], while here the proposed sizes of nanowire and nanodot are
creases sharply from the point A4 to the point A5, and then decreases about 55 × 1000 × 41 nm and 55 × 55 × 41 nm, respectively). The
slightly from the points A5 to A7. The increase of G at the point A5 memory capacity of FRAM expected can increase considerably in the
explained is due to the remained polarizations after removing the ex- next generations.
ternal electric fields. Remarkably, at the point A7, the new single po-
larization vortex is formed, in which the vortex chirality is opposite to 4. Conclusions
the initial one (A1). This obtained result shows that the single polar-
ization vortex can form and switch in the nanodot by the asymmetrical In summary, the present study proposes a new approach to form and
pair of the external electric field. At the last two stages of switch the single polarization vortex in ferroelectric nanowires and
(A7→A8→A9→A10) and (A10→A11→A12→A1), with the same pro- nanodots by the direct electric field. The reduction in the physical size
cess as the first and the second stages, the vortex chirality is switched of the memory cell based on the polarization vortex makes the storage
(from the domain structure A7 to the domain structure A1) by changing capacity of FRAM per an area unit increase significantly. These results

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D. Van Truong, et al. Materials Research Bulletin 131 (2020) 110981

Fig. 4. Domain evolution of nanodot under a rectangular waveform of the asymmetrical pair of the external electric field. (a) Relationship between the toroidal
moment G and the external electric field E. The evolution direction is illustrated by several key points from A1 to A12. (b) The corresponding domain structure from
point A1 to A12.

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magnitude and stability of ferroelectric polarization in ultrathin PbTiO3 films from
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The authors declare that they have no known competing financial
1.4816350.
interests or personal relationships that could have appeared to influ- [17] I. Ponomareva, I.I. Naumov, L. Bellaiche, Low-dimensional ferroelectrics under
ence the work reported in this paper. different electrical and mechanical boundary conditions: atomistic simulations,
Phys. Rev. B 72 (2005) 214118, , https://doi.org/10.1103/physrevb.72.214118.
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This research was funded by the Vietnam's National Foundation for [19] J. Wang, Switching mechanism of polarization vortex in single-crystal ferroelectric
nanodots, Appl. Phys. Lett. 97 (2010) 192901, , https://doi.org/10.1063/1.
Science and Technology Development (NAFOSTED) with No.107.02- 3515847.
2016.18; [20] L.V. Lich, T. Shimada, J. Wang, T. Kitamura, Instability criterion for ferroelectrics
under mechanical/electric multi-fields: ginzburg-Landau theory based modeling,
Acta Mater. 112 (2016) 1–10, https://doi.org/10.1016/j.actamat.2016.03.081.
Appendix A. Supplementary data [21] S. Prosandeev, I. Ponomareva, I. Kornev, L. Bellaiche, Control of vortices by
homogeneous fields in asymmetric ferroelectric and ferromagnetic rings, Phys. Rev.
Supplementary material related to this article can be found, in the Lett. 100 (2008) 047201, , https://doi.org/10.1103/physrevlett.100.047201.
[22] W.J. Chen, Y. Zheng, B. Wang, J.Y. Liu, Coexistence of toroidal and polar domains
online version, at doi:https://doi.org/10.1016/j.materresbull.2020.
in ferroelectric systems: a strategy for switching ferroelectric vortex, J. Appl. Phys.
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