Abstract
Intrinsic polar metals are rare, especially in oxides, because free electrons screen electric fields in a metal and eliminate the internal dipoles that are needed to break inversion symmetry. Here we use firstprinciples highthroughput structure screening to predict a new polar metal in bulk and thin film forms. After screening more than 1000 different crystal structures, we find that ordered BiPbTi_{2}O_{6} can crystallize in three polar and metallic structures, which can be transformed between via pressure or strain. In a heterostructure of layered BiPbTi_{2}O_{6} and PbTiO_{3}, multiple states with different relative orientations of BiPbTi_{2}O_{6} polar displacements, and PbTiO_{3} polarization, can be stabilized. At room temperature, the interfacial coupling enables electric fields to first switch PbTiO_{3} polarization and subsequently drive 180° change of BiPbTi_{2}O_{6} polar displacements. At low temperatures, the heterostructure provides a tunable tunnelling barrier and might be used in multistate memory devices.
Introduction
Polar metals–analogy of ferroelectrics in metals–are characterized by intrinsic conduction and inversion symmetry breaking. Polar metals are rare (especially in oxides) because mobile electrons screen electric fields in a metal and eliminate internal dipoles that are needed to break inversion symmetry. The discovery of LiOsO_{3}^{1}, a metal that transforms from a centrosymmetric \(R{\bar{3}}c\) structure to a polar \(R{3}c\) structure at 140 K, has stimulated an active search for new polar metals in both theory and experiment^{2,3,4,5,6,7,8,9}.
Densityfunctionaltheorybased firstprinciples calculations have proven accurate in describing crystal structures and have been succesfully applied to predict new functional materials, such as ferroelectrics, piezoelectrics and multiferroics^{10}. Since crystal structure is the essential property of polar metals, we need to scrutinize the prediction by not presupposing an a priori favorable crystal structure. Firstprinciples highthroughput crystal structure screening method, which is based on the marriage between firstprinciples calculations and a multitude of techniques such as particleswarm optimization algorithm^{11} and evolutionary algorithm^{12}, has demonstrated its superior power in effectively searching for the ground state structures and metastable structures of functional materials with only the given knowledge of chemical composition^{13,14,15}.
In this work, we use ab initio highthroughput structure screening to predict a new polar metal BiPbTi_{2}O_{6} (BPTO for short). After screening over 1000 different crystal structures, we find that ordered BPTO can crystallize in three different polar metallic structures (postperovskite \(Pmm2\), perovskite \(Pmm2\) and perovskite \(Pmn{2}_{1}\)), each of which can be transformed to another via external pressure or epitaxial strain. The mechanism is that \(6s\) lone–pair electrons of Bi and Pb ions tend to favor offcenter displacements^{10}. On the other hand, in the perovskite structures, Bi^{3+} and Pb^{2+} enforce a fractional valence on Ti, which leads to conduction; in the postperovskite structure, strong hybridization between Bi/Pb \(6p\) and O \(2p\) states induces a finite density of states at the Fermi level.
Next we demonstate potential applications of the new polar metal BPTO by studying a BPTO/PbTiO_{3} heterostructure. We find that different states in which BPTO polar displacements are parallel, antiparallel and perpendicular to PbTiO_{3} polarization can be stabilized in the heterostructure. Also, 180° switching of BPTO polar displacements needs to surmount an energy barrier of about 58 meV per slab. This implies that at room temperature where thermal fluctuations can overcome the switching barrier, the interfacial coupling between the polarization and polar displacements enables an electric field to first switch PbTiO_{3} polarization and subsequently drive BPTO to change its polar displacements by 180°; at low temperatures where the switching barrier dominates over thermal fluctuations, the BPTO polar displacements can not be switched but the direction of PbTiO_{3} polarization can be controlled by an electric field. This can stabilize three distinct states with different tunnelling barriers.
Results and discussion
Most stable crystal structures of bulk BPTO
The key question in predicting a new polar metal is to determine its crystal structure. Since ordered BPTO has not been synthesized in experiment, we perform a firstprinciples highthroughput search for the ground state structure using CALYPSO^{11,16} method, in combination with CrySPY^{17}. In the search, we do not constrain ourselves in any a priori favorable crystal structure. We screen >1000 different crystal structures among which we consider different Bi/Pb ordering in perovskite structure: layered ordering, columnar ordering and rocksalt ordering; and we also consider many nonperovskite structures, including postperovskite structure and hexagonal structure. The computational details of our firstprinciples calculations and highthroughput structure screening method are provided in Methods.
Figure 1 shows ten lowestenergy crystal structures of BPTO from our calculations. The details of these ten crystal structures are available in Supplementary Table 1. The lowest energy structure is postperovskite with a polar symmetry \(Pmm2\) (space group No. 25). The crystal structure is explicitly shown in Fig. 1b. The TiO_{6} octahedra are both cornersharing and edgesharing. The lack of inversion symmetry can be appreciated from Ti atoms which have strong polar displacements with respect to neighboring O atoms towards \(x\)axis. The next two lowestenergy crystal structures are both perovskite with \(Pmn{2}_{1}\) symmetry (space group No. 31) and \(Pmm2\) symmetry (space group No. 25). Both \(Pmn{2}_{1}\) and \(Pmm2\) symmetries are polar. The two perovskite structures have almost the same energy. Figure 1c shows the perovskite \(Pmn{2}_{1}\) crystal structure. Bi and Pb atoms form a rocksalt ordering and their displacements with respect to O atoms in the \(xy\) plane make the crystal structure acentric. Figure 1d shows the perovskite \(Pmm2\) crystal structure. Bi and Pb atoms have a layered ordering with a stacking direction along \(z\)axis. It is clear that Bi, Pb, and Ti atoms all have strong polar displacements with respect to O atoms along \(x\)axis, which breaks inversion symmetry. While postperovskite oxides are interesting by themselves^{18,19}, perovskite oxides have been widely studied and are more suitable for device applications because many perovskite oxide substrates are available^{20}, which makes it feasible to grow perovskite oxide thin films. Therefore, we consider using external pressure or epitaxial strain to transform BPTO among different polar structures. Pressure is widely used in bulk synthesis to isolate metastable phases of matter^{21,22}. Figure 1e shows that both perovskite \(Pmn{2}_{1}\) and \(Pmm2\) structures become more stable than the postperovskite \(Pmm2\) structure under a few GPa. The reason is that the postperovskite \(Pmm2\) structure is very hollow with a very large volume of 130 \({\mathrm{\AA}}^{3}\) f.u.\({}^{1}\) under ambient conditions, while the two perovskite structures are more closely packed (122 \({\mathrm{\AA}}^{3}\) f.u.\({}^{1}\) and 126 \({\mathrm{\AA}}^{3}\) f.u.\({}^{1}\) under ambient conditions, respectively). Applying pressure favors structures with smaller volumes. If we want to grow BPTO thin films on a perovskite oxide substrate, the postperovskite structure does not form due to very large lattice mismatch (see Supplementary Table 1 for the cell parameters of postperovskite structure). The pseudocubic lattice constant of the perovskite \(Pmn{2}_{1}\) structure is 3.94 Å, while that of the perovskite \(Pmm2\) structure is 3.98 Å. It is anticipated that as the substrate lattice constant varies from 3.94 Å to 3.98 Å, the energetically favored structure changes from the perovskite \(Pmn{2}_{1}\) structure to the perovskite \(Pmm2\) structure. This is indeed what Fig. 1f shows. Since the perovskite \(Pmm2\) structure has a layered ordering of Bi/Pb atoms, it is highly suitable for thin film growth methods such as pulsed layer deposition and molecular beam epitaxy^{23}. Substrates such as NdScO_{3} and KTaO_{3} have a proper lattice constant to stabilize the perovskite \(Pmm2\) structure in BPTO thin films. The DFT calculated lattice constants of KTaO_{3} and NdScO_{3} can be found in Supplementary Table 2 with the comparison to the experimental data. We also enforce the postperovskite \(Pmm2\) structure to be stabilized on a perovskite oxide substrate and we expectedly find that its total energy is about 10 eV f.u.\({}^{1}\) higher than the two perovskite structures because of the large lattice mismatch (Supplementary Fig. 1). In addition to the study of phase transitions under strains and pressures, the temperature effect on phase transitions can be found in Supplementary Fig. 2.
Electronic and magnetic properties of polar metal BPTO
The upper panels of Fig. 2 show the DFTcalculated densities of states of the postperovskite \(Pmm2\), perovskite \(Pmn{2}_{1}\) and perovskite \(Pmm2\) structures. We calculate both total density of states (DOS) and orbitalprojected DOS (Ti\(3d\), Bi\(6s\), Pb\(6s\), and O\(2p\)). In three optimized structures, we do not find any magnetization or charge disproportionation. Therefore spinup and spindown are summed in the DOS. The DOS projected on the two Ti atoms are identical and hence are also summed. The three DOS share similarities but also have important differences. All three structures have a nonzero DOS at the Fermi level; both Bi\(6s\) and Pb\(6s\) are well below the Fermi level and are fully occupied. The difference is that in both perovskite structures (\(Pmn{2}_{1}\) and \(Pmm2\)), because nominally Bi\({}^{3+}\), Pb\({}^{2+}\) and O\({}^{2}\), due to charge neutrality Ti must have a formal valence of Ti\({}^{3.5+}\), i.e., every Ti atom has 0.5 electron in the \(3d\) conduction bands (no charge disproportionation is found in the calculations). Figure 2b, c shows that the Fermi level crosses Ti\(3d\) states in the DOS of the perovskite \(Pmn{2}_{1}\) and \(Pmm2\) structures. However, in the postperovskite structure (Fig. 2a), Ti\(3d\) states have negligible contribution around the Fermi level. Instead, Bi\(6p\) and Pb\(6p\), as well as O\(2p\) states make the largest contribution to the DOS around the Fermi level, which can also be seen in Supplementary Fig. 3 where the electronic states around the Fermi level are zoomed in.
The Bader (static) charge analysis in Table 1 shows that Bi and Pb have about 0.25 and 0.19 more electrons in the postperovskite structure than in the perovskite structures, which indicates stronger hybridization between Bi/Pb and O atoms in the postperovskite structure. Therefore in the postperovskite structure, Bi\(6p\) and Pb\(6p\) states are not fully empty and thus appear around the Fermi level.
Pb and Bi are heavy elements and their spin–orbit interactions (SOI) are not negligible. In the lower panels of Fig. 2, we take into account SOI and show the corresponding densities of states of BPTO of the three polar structures. Similar to the results without SOI, we do not find any magnization or charge disproportionation in the fully relaxed structures. By comparing the densities of states calculated by DFT without SOI (upper panels of Fig. 2) and DFT with SOI (lower panels of Fig. 2), SOI almost unaffects the electronic structure, similar to previous studies on other polar metals^{3,24}.
While DFT with/without SOI calculations do not find any magnetization or charge disproportionation, correlation effects from Ti\(3d\) orbitals may favor spin ordering and charge ordering. A longrange magnetic ordering with a charge disproportionation (Ti\({}^{3+}\)+Ti\({}^{4+}\)) can result in an insulating ground state^{25}. To test the robustness of our prediction that BiPbTi_{2}O_{6} is a polar metal, we apply an effective Hubbard \(U\) correction on the Ti3\(d\) orbitals and calculate the densities of states for all three lowenergy structures. The accurate value of correlation strength of BPTO is not known, but presumably it should not exceed that of Mott insulator LaTiO_{3}, in which Hubbard \({U}_{{\rm{Ti}}}\) is about 5 eV^{26}. Therefore we consider a Hubbard \({U}_{{\rm{Ti}}}\) ranging from 0 to 5 eV. Within this range of \({U}_{{\rm{Ti}}}\), we do not find charge disproportionation but find robust metallicity in all the three polar structures of BPTO. Furthermore, in this range of \({U}_{{\rm{Ti}}}\), we find itinerant ferromagnetism in the perovskite \(Pmn{2}_{1}\) structure at \({U}_{{\rm{Ti}}}\ge 1\) eV and in the perovskite \(Pmm2\) structure at \({U}_{{\rm{Ti}}}\ge 2\) eV (antiferromagnetic ordering is less stable than ferromagnetic ordering). We do not find any magnetism in the postperovskite \(Pmm2\) structure up to \({U}_{{\rm{Ti}}}=5\) eV. The magnetic phase diagram for the three polar structures as a function of Hubbard \({U}_{{\rm{Ti}}}\) is shown in Fig. 3. The origin of itinerant ferromagnetism in BPTO is Stoner instability^{27}. In DFT+\(U\) calculations, the Stoner criterion to induce itinerant ferromagnetism is^{28}:
were \(U\) and \(\rho ({E}_{{\rm{F}}})\) are Hubbard \(U\) parameter and density of states at the Fermi level of a nonmagnetic state, respectively. The upper panels of Fig. 2 shows that the perovskite \(Pmn{2}_{1}\) structure has a large density of state at the Fermi level \(\rho ({E}_{{\rm{F}}})\) in its nonmagnetic state; the perovskite \(Pmm2\) structure has a slightly smaller \(\rho ({E}_{{\rm{F}}})\). Postperovskite \(Pmm2\) structure, on the other hand, has a very small \(\rho ({E}_{{\rm{F}}})\) (9 times smaller than that of the perovskite \(Pmm2\) structure and 15 times smaller than that of the perovskite \(Pmn{2}_{1}\) structure). This explains that the critical \({U}_{{\rm{Ti}}}\) to stabilize itinerant ferromagnetism in the perovskite \(Pmn{2}_{1}\) structure is the smallest, while a much larger \({U}_{{\rm{Ti}}}\) (larger than 5 eV) is needed to induce magnetism in the postperovskite \(Pmm2\) structure.
The role of lonepair electrons
A local structural instability arising from lonepair electrons has been reported in ferroelectric insulators and degenerately doped ferroelectrics^{10,29,30,31,32,33,34,35}. However, lonepair electrons alone are not sufficient to stabilize a polar state in metals nor a ferroelectric state in insulators. For example, BiFeO_{3} is ferroelectric^{30} but BiMnO_{3} is antiferroelectric^{36,37} although lonepair electrons are present in both of them. Therefore, highthroughput crystal structure prediction is essential in predicting new polar metals and ferroelectric insulators. In our study, the crystal structure screening takes into account both polar and antipolar states for different cation orderings.
We now show that in the three lowestenergy metallic phases of BPTO, the lone–pair \(6s\) electrons in Bi and Pb play an important role in breaking inversion symmetry. We use electron localization function (ELF, defined in Methods) to explicitly visualize how lone–pair electrons of Bi and Pb break inversion symmetry in metallic BPTO. Figure 4a–c shows an isosurface of ELF of the three polar structures of BPTO. Only the ELF of Bi and Pb ions are displayed for clarity. Similar to insulating Bibased and Pbbased perovskite oxides^{29,30,38}, the ELF shows that a lobelike lonepair resides on one side of Bi and Pb ions in all three polar metallic structures, which is the driving force to break inversion symmetry. On the other hand, ELF in the corresponding centrosymmetric structures shows sphericalsymmetric feature, which is implied in Fig. 4d–f. Furthermore, we calculate the total energy variation as a function of normalized polar displacement \(\lambda\) from the centrosymmetric structures to the polar structures (see Fig. 4g–i). In all three cases, the energy curve monotonically decreases from the centrosymmetric structure to the polar structure, which indicates a continuous and spontaneous phase transition below a critical temperature (satisfying Anderson’s and Blount’s criterion of a ferroelectriclike metal^{39}). The energy difference between the polar structure and the corresponding centrosymmetric structure of BPTO in all three cases is larger than that of LiOsO_{3} (about 25 meV f.u.\({}^{1}\)), implying that the structural transition temperature of BPTO is higher than that of LiOsO_{3}^{40}. We note that the above secondorder structural phase transition is a key property to distinguish instrinsic polar metals from degenerately doped ferroelectrics^{32,33,34,35,41,42}, because realistic dopants (cation substitution or oxygen vacancies) make the crystal symmetry of doped ferroelectrics illdefined and correspondingly there is no welldefined continuous structural phase transition at finite temperatures.
Switching barrier of BPTO thin films in a heterostructure
Next we study BPTO thin films. The \(Pmm2\) perovskite structure of BPTO, which has a layered Bi/Pb ordering, is highly suitable for thin film growth and can be stabilized on a perovskite oxide substrate having a lattice constant of 3.98 Å or larger. The Bi/Pb stacking direction in the \(Pmm2\) perovskite structure is chosen as the \(z\)axis, while the polar displacements are in the \(xy\)plane. In addition, we find that constrained by an inplane lattice constant of 3.98 Å or larger, ferroelectric PbTiO_{3} is under tensile strain and favors an inplane polarization over an outofplane polarization (Supplementary Fig. 4). Therefore, we study a BPTO/PbTiO_{3} heterostructure, in which both BPTO polar displacements and PbTiO_{3} polarization are parallel to the interface. We will show that different from previously studied ferroelectric/polarmetal heterostructures^{2,4,43,44}, multiple states with different relative orientations of BiPbTi_{2}O_{6} polar displacements and PbTiO_{3} polarization can be stabilized. When an electric field is applied to switch the polarization of PbTiO_{3}, a finite energy barrier exists for BPTO to change its polar displacements by 180°. If the temperature is high enough that thermal fluctuations can overcome the energy barrier, the polar displacements of BPTO will follow the change of PbTiO_{3} polarization. Otherwise, the polar displacements of BPTO stay put and form different configurations when the external electric field changes the direction of PbTiO_{3} polarization.
Figure 5a shows a BPTO/PbTiO_{3} heterostructure. The inplane lattice constant is constrained to 4 Å, which stabilizes both perovskite \(Pmm2\) structure of BPTO and an inplane polarization of PbTiO_{3}. Experimentally substrates such as KTaO_{3} and NdScO_{3} can provide such a lattice constant. Figure 5a shows two different configurations: on the left (right) is a “parallel state” (“antiparallel state”) in which PbTiO_{3} polarization is parallel (antiparallel) to BPTO polar displacements. Both configurations are stabilized after relaxation in our calculations. We first find that oneunitcell thin film of BPTO is still polar and metallic. Figure 5b shows layerresolved conduction electrons by integrating the partial density states of Ti\(d\) orbitals (Supplementary Fig. 5). Conduction electrons are mainly confined in BPTO with some charge leakage into a few unit cells of PbTiO3. This charge leakage is due to the proximate effect that Ti\(d\) states in PbTiO_{3} are empty while Ti\(d\) states in BPTO nominally have 0.5\(e\) per Ti atom. Such a charge leakage can be effectively prevented by replacing PbTiO_{3} with PbTi\({}_{1x}\)Zr\({}_{x}\)O_{3}^{45}, which is supported by our calculations in Supplementary Fig. 6. Figure 5c shows the layerresolved cation displacements of Ti and Pb/Bi with respect to O atoms along the \(x\)axis. The polar displacements of Bi and Pb in BPTO are almost bulklike in both configurations. We note that the polar property of BPTO is not due to the interfacial coupling with PbTiO_{3} (Supplementary Fig. 7). With PbTiO_{3} replaced by a paraelectric SrTiO_{3} substrate, oneunitcell BPTO layer still has polar displacements and is metallic (Supplementary Fig. 8).
Next we study thermodynamics and the energy barrier of switching between “parallel state” and “antiparallel state”. DFT calculations find that the energy of “parallel state” is 37 meV per slab lower than that of “antiparallel state”. This is because in “antiparallel state”, a 180° domain wall is formed in PbTiO_{3} close to the interface, which is clearly seen from Fig. 5c. Forming such a 180° domain wall in ferroelectrics increases energy^{46,47}. Figure 5c shows that in both configurations, the interface strongly favors a parallel coupling between BPTO polar displacements and PbTiO_{3} polarization.
While “parallel state” is more stable than “antiparallel state”, “antiparallel state” can be stabilized by itself because it is a local minimum. Therefore a finite energy barrier exists for BPTO to 180° change its polar displacements from “antiparallel state” to “parallel state”. To quantitatively calculate the energy barrier and identify a possible switching path for polar displacement, we perform the climbing image nudged elastic band (NEB) calculations^{48} and use transition state theory^{49}. Transition state theory has been widely used in understanding polarization switching in ferroelectric thin films^{50,51}, as well as ferroelectric domain wall motion^{52}. We choose “antiparallel state” as the initial state and “parallel state” as the final state. We study a possible switching path in which BPTO polar displacements are 180° “rotated” in the \(xy\) plane. The NEB results are shown in Fig. 5d. Along the structural transition path from “antiparallel state” (labelled as “1”) to “parallel state” (labelled as “3”), there is another metastable state (labelled as “2”) where BPTO polar displacements are perpendicular to PbTiO_{3} polarization in the \(xy\) plane (Fig. 5e). Between the three stable states (“1”, “2”, “3”), there are two energy barriers. The larger one, i.e., the energy difference between the antiparallel state and the highest saddle point, is 58 meV per slab.
Multifunctions of the BPTO/PTO heterostructure
In this section, we discuss potential functions of the BPTO/PTO heterostructure based on the calculated switching barrier in the previous section.
We first discuss room temperature applications. The switching barrier of BPTO is about 58 meV per slab. From transition state theory^{49}, at a given temperature \(T\), an energy barrier \(\Delta E\) with a magnitude of a few \({k}_{{\rm{B}}}T\) can be easily surmounted [At room temperature, 1 \({k}_{{\rm{B}}}T\approx\) 26 meV. In transition state theory, the probability \(P\) of overcoming the energy barrier is proportional to e\({}^{\Delta E/{k}_{{\rm{B}}}T}\), i.e., \(P\)\(\propto\) e\({}^{\Delta E/{k}_{{\rm{B}}}T}\). The energy barrier (\(\Delta E\) = 58 meV) is about twice the \({k}_{{\rm{B}}}T\), hence the probability of overcoming this barrier is around 14\(\%\).] (\({k}_{{\rm{B}}}\) is the Boltzmann constant). Room temperature \(T=300\) K is about 26 meV. Our energy barrier is about twice room temperature and therefore room temperature is sufficient to overcome the barrier. This implies that the interfacial coupling at the BPTO/PbTiO_{3} interface enables an electric field to first switch PbTiO_{3} polarization and subsequently drive BPTO to 180° change its polar displacements. This realizes an electrically switchable bistate in the new polar metal BPTOat room temperature. We note that the transition path chosen in the NEB calculation is only one possiblity. The actual transition path could be different from the one in our study and the resulting energy barrier should be even lower, which will make the switching of BPTO polar displacements more feasible. Figure 6a schematically shows how we can use PbTiO_{3} polarization to control the polar displacements of BPTO at room temperature.
The above switching mechanism is also applicable to multilayer BPTO thin films. The mechanism is as follows. Our calculations find that bulk BPTO is more stable in the polar \(Pmm2\) perovskite structure than the antipolar \(Pmma\) perovskite structure by 65 meV f.u.\({}^{1}\). The antipolar \(Pmma\) perovskite structure is shown in Fig. 7a. The polar \(Pmm2\) perovskite structure is shown in Fig. 7b for comparison. Therefore, for multilayer BPTO thin films, once the bottom layer of BPTO is 180° switched via the interfacial coupling, the remaining layers of BPTO will be driven by thermodynamics to change their polar displacements in a layerbylayer manner to avoid an antipolar state in the film. The above physical picture is computationally confirmed in Supplementary Fig. 9. However, for device applications (e.g. the model device illustrated in Supplementary Fig. 10), BPTO thin films of singleunitcell thick are most desirable, in analogy to twodimensional Van der Waals materials^{9}.
Next we discuss low temperature applications. At sufficiently low temperatures where the energy barrier is much larger than \({k}_{{\rm{B}}}T\), the interfacial coupling can not drive polar metals to change their polar displacements when an electric field switches the polarization of ferroelectrics. However, this has interesting implications: as we use the electric field to change the direction of PbTiO_{3} polarization, we can individually stabilize multiple configurations in which the BPTO polar displacements are “parallel”, “perpendicular” and “antiparallel” to the PbTiO_{3} polarization (shown in Fig. 6b). Each configuration has different tunnelling resistance across ferroelectric insulators, because BPTO polar displacements and PbTiO_{3} polarization have different relative orientation. As we use an electric field to change the direction of ferroelectric polarization (polar displacements do not follow due to low temperatures), we can tune tunnelling barriers between different states and therefore the BPTO/PbTiO_{3} heterostructure can be used in multistate memory devices.
In conclusion, we demonstrate the power of firstprinciples highthroughput screening in designing new functional materials and in particular predict a new polar metal BPTO by utilizing the Bi/Pb lonepair electrons. The three lowestenergy structures of BPTO are all polar and metallic (postperovskite \(Pmm2\), perovskite \(Pmm2\) and perovskite \(Pmn{2}_{1}\)), which can be transformed among each other via pressure or strain. In the perovskite structures, Bi\({}^{3+}\) and Pb\({}^{2+}\) enforce a fractional valence \(3.5+\) on Ti, which leads to conduction. In the postperovskite structure, strong hybridization between Pb/Bi \(6p\) and O \(2p\) states induces a finite density of states at the Fermi level. In a BPTO/PbTiO_{3} heterostructures, at room temperature the interfacial coupling can overcome the switching barrier, which enables an electric field to first switch PbTiO_{3} polarization and subsequently drive BPTO to 180° flip its polar displacements. This realizes an electrically switchable bistate in the new polar metal BPTO. The switching method is applicable to other layered polar metals^{3}. At low temperature, an electric field can control the direction of PbTiO_{3} polarization and stabilize multi states in which PbTiO_{3} polarization and BPTO polar displacements have different relative orientations, implying different tunnelling resistance. This property can be used in tunable multistate memory devices. We hope this work will stimulate experimentalists to synthesize the new polar metal in both bulk and thinfilm forms.
Methods
Firstprinciples calculations
For bulk structures, density functional theory (DFT) calculations are performed using a plane wave basis set and projectoraugmented wave method^{53}, as implemented in the Vienna Abinitio Simulation Package (VASP)^{54,55}. PBEsol, a revised Perdew–Burke–Ernzerhof (PBE) generalized gradient approximation for improving equilibrium properties of denselypacked solids^{56}, is used as the exchange correlation functional and has been applied successfully to interpreting the experimental observations of polar metal LiOsO_{3} in our previous work^{24}. The Brillouin zone integration is performed with a Gaussian smearing of 0.05 eV over a \(\Gamma\)centered kmesh up to 12 × 12 × 12 and a 600 eV planewave cutoff. The threshold of energy convergence is 10−6 eV. Hubbard \(U\) corrections are also considered in our calculations to model the effects of strong correlation on electronic and magnetic properties. The rotationally invariant approach of Hubbard \(U\) proposed by Dudarev et al.^{57} is used in our DFT+\(U\) calculations. Spinorbit coupling (SOC) is also considered to study electronic structure in our DFT+\(U\)+SOC calculations^{58}.
For the calculations of BPTO/PbTiO_{3} structures, a \(\Gamma\)centered kmesh of 10 × 10 × 1 is used. The periodic slabs are separated by vacuum of 20 Å thick to diminish the interaction between them. Since asymmetrical interface modelling is used in our calculations, we employ dipole correction to eliminate the artificial electric field in the vacuum^{59,60}. In all the interface calculations, the inplane lattice constant is fixed to be 4 Å and the bottom layer of PbTiO_{3} is fixed to simulate the bulklike interior that is under tensile strain. All the other atoms are fully relaxed along the three axes. We consider two possible terminations of the heterostructure, i.e., BaO and BiOterminations. The former one is less stable than the latter one by ~220 meV per slab. Hence, we only report the BiOterminated BPTO/PbTiO_{3} interface in our study.
The energy barriers between the parallel and antiparallel states, as well as the saddle points along the transition path are found by the nudged elastic band (NEB) calculations through the climbing image NEB method^{48}. In NEB calculations, a set of intermediate structures (i.e., images) between the initial state (antiparallel state) and the final state (parallel state) are generated. They are iteratively adjusted so as to minimize the increase in energy along the transition path.
The electron localization function in our study, which is used to visualize lone–pair electrons in the real space is defined as^{61}:
where
and
Here \(\rho\) is the electron density and \({\phi }_{i}\) are the Kohn–Sham wave functions.
Crystal structure search
The crystal structure search for bulk BPTO is carried out using the particle swarm optimization algorithm implemented in CALYPSO code^{11,16}, with the assistance of CrySPY^{17}. More than 1000 structures (50% 10atom BiPbTi_{2}O_{6} and 50% 20atom Bi_{2}Pb_{2}Ti_{4}O_{12}) are created in 20 generations. The structural optimization and computation of total energy are performed using VASP. In the first step of highthroughput screening of these 1000 crystal structure, we used nonspin polarized calculations with the exchangecorrelation functional of PBEsol. The cutoff energy of 450 eV and the kmesh grid density is about 2000 per atom. In the second step, the lowest 50 structures are recalculated by the spinpolarized calculations in which the cutoff energy is increased to 600 eV and the kmesh grid density is >2500 per atom. We consider ferromagnetic ordering and different types of antiferromagnetic orderings such as \(A\)type, \(C\)type and \(G\)type^{62} to examine possible magnetic properties. The global structure search is performed under 0 GPa. The five lowest energy structures after screening are also studied under pressure. The space groups of the predicted crystal structures are examined by the FINDSYM code^{63}.
Visualization
We use software VESTA to show crystal structures and realspace electron localized functions^{64}.
Data availability
The authors declare that all the data supporting the findings of this study are available within the paper and its Supplementary Information.
Code availability
The highthroughput crystal structural predictions were carried out using the proprietary code VASP^{54,55}, with the combination of CALYPSO^{11,16} and CrySPY^{17}. CALYPSO (http://www.calypso.cn/) is freely distributed on academic use under the license of Copyright Protection Center of China (registration No. 2010SR028200 and classification No. 610007500). CrySPY (https://github.com/TomokiYAMASHITA/CrySPY) is released under the Massachusetts Institute of Technology (MIT) License and is open source. The electronic structure calculations were all performed using VASP. The thermal properties are calculated by Phonopy^{65}. Phonopy (https://github.com/atztogo/phonopy) is released under the BSD3Clause License and is open source. The software VESTA^{64} is distributed free of charge for academic users under the VESTA License (https://jpminerals.org/vesta/jp/download.htm).
References
 1.
Shi, Y. et al. A ferroelectriclike structural transition in a metal. Nat. Mater. 12, 1024–1027 (2013).
 2.
Xiang, H. J. Origin of polar distortion in LiNbO_{3} type “ferroelectric” metals: Role of Asite instability and shortrange interactions. Phys. Rev. B 90, 094108 (2014).
 3.
Puggioni, D. & Rondinelli, J. M. Designing a robustly metallic noncenstrosymmetric ruthenate oxide with large thermopower anisotropy. Nat. Commun. 5, 3432 (2014).
 4.
Filippetti, A., Fiorentini, V., Ricci, F., Delugas, P. & Íñiguez, J. Prediction of a native ferroelectric metal. Nat. Commun. 7, 11211 (2016).
 5.
Kim, T. et al. Polar metals by geometric design. Nature 533, 68 (2016).
 6.
Benedek, N. A. & Birol, T. ‘ferroelectric’ metals reexamined: fundamental mechanisms and design considerations for new materials. J. Mater. Chem. C 4, 4000–4015 (2016).
 7.
Luo, W., Xu, K. & Xiang, H. Twodimensional hyperferroelectric metals: A different route to ferromagneticferroelectric multiferroics. Phys. Rev. B 96, 235415 (2017).
 8.
Mochizuki, Y., Kumagai, Y., Akamatsu, H. & Oba, F. Polar metallic behavior of strained antiperovskites \(A\) CNi\(A\) (\(A\) = Mg, Zn, and Cd) from first principles. Phys. Rev. Materials 2, 125004 (2018).
 9.
Fei, Z. et al. Ferroelectric switching of a twodimensional metal. Nature 560, 336 (2018).
 10.
Fang, Y.W. et al. Firstprinciples studies of multiferroic and magnetoelectric materials. Sci. Bull. 60, 156–181 (2015).
 11.
Wang, Y., Lv, J., Zhu, L. & Ma, Y. Calypso: a method for crystal structure prediction. Comput. Phys. Commun. 183, 2063–2070 (2012).
 12.
Glass, C. W., Oganov, A. R. & Hansen, N. USPEXEvolutionary crystal structure prediction. Comput. Phys. Commun. 175, 713–720 (2006).
 13.
Wei, Y. et al. A rhombohedral ferroelectric phase in epitaxially strained Hf\({}_{0.5}\) Zr\({}_{0.5}\)O\({}_{0.5}\) thin films. Nat. Mater. 17, 1095–1100 (2018).
 14.
He, J., Xia, Y., Naghavi, S. S., Ozoliņš, V. & Wolverton, C. Designing chemical analogs to PbTe with intrinsic high band degeneracy and low lattice thermal conductivity. Nat. Commun. 10, 719 (2019).
 15.
Zhao, Z. et al. Predicted pressureinduced superconducting transition in electride Li\({}_{6}\)P. Phys. Rev. Lett. 122, 097002 (2019).
 16.
Wang, Y., Lv, J., Zhu, L. & Ma, Y. Crystal structure prediction via particleswarm optimization. Phys. Rev. B 82, 094116 (2010).
 17.
Yamashita, T. et al. Crystal structure prediction accelerated by bayesian optimization. Phys. Rev. Mater. 2, 013803 (2018).
 18.
Murakami, M., Hirose, K., Kawamura, K., Sata, N. & Ohishi, Y. Postperovskite phase transition in MgSiO_{3}. Science 304, 855–858 (2004).
 19.
Ohta, K. et al. The electrical conductivity of postperovskite in earth’s D” layer. Science 320, 89–91 (2008).
 20.
Biswas, A., Yang, C.H., Ramesh, R. & Jeong, Y. H. Atomically flat single terminated oxide substrate surfaces. Prog. Surf. Sci. 92, 117–141 (2017).
 21.
Zhang, Z. et al. Highpressure bulk synthesis of crystalline C\({}_{6}\)N\({}_{9}\)H\({}_{3}\cdot\)HCl: a novel C_{3}N_{4} graphitic derivative. J. Am. Chem. Soc. 123, 7788–7796 (2001).
 22.
Klein, R. A. et al. Highpressure synthesis of the BiVO_{3} perovskite. Phys. Rev. Mater. 3, 064411 (2019).
 23.
Korotcenkov, G. Metal Oxidebased Thin Film Structures: Formation, Characterization and Application of Interfacebased Phenomena, (Elsevier, 2017).
 24.
Aulesti, E. I. P. et al. Pressureinduced enhancement of nonpolar to polar transition temperature in metallic LiOsO_{3}. Appl. Phys. Lett. 113, 12902 (2018).
 25.
Pentcheva, R. & Pickett, W. E. Correlationdriven charge order at the interface between a mott and a band insulator. Phys. Rev. Lett. 99, 016802 (2007).
 26.
Pavarini, E. et al. Mott transition and suppression of orbital fluctuations in orthorhombic \(3{d}^{1}\) perovskites. Phys. Rev. Lett. 92, 176403 (2004).
 27.
Fazekas, P. Lecture notes on electron correlation and magnetism, (World scientific, 1999).
 28.
Janicka, K., Velev, J. P. & Tsymbal, E. Y. Magnetism of LaAlO_{3} /SrTiO_{3} superlattices. J. Appl. Phys. 103, 07B508 (2008).
 29.
Cohen, R. E. Origin of ferroelectricity in perovskite oxides. Nature 358, 136 (1992).
 30.
Ravindran, P., Vidya, R., Kjekshus, A., FjellvÅg, H. & Eriksson, O. Theoretical investigation of magnetoelectric behavior in BiFeO\({}_{3}\). Phys. Rev. B 74, 224412 (2006).
 31.
Luo, W. & Xiang, H. Twodimensional phosphorus oxides as energy and information materials. Angew. Chem. 128, 8717–8722 (2016).
 32.
Zhao, H. J. et al. Metascreening and permanence of polar distortion in metallized ferroelectrics. Phys. Rev. B 97, 054107 (2018).
 33.
Gu, J.x et al. Coexistence of polar distortion and metallicity in PbTi\({}_{1x}\)Nb\({}_{1x}\) O\({}_{1x}\). Phys. Rev. B 96, 165206 (2017).
 34.
He, X. & Jin, K.j Persistence of polar distortion with electron doping in lonepair driven ferroelectrics. Phys. Rev. B 94, 224107 (2016).
 35.
Shen, X.W., Fang, Y.W., Tian, B.B. & Duan, C.G. Twodimensional ferroelectric tunnel junction: the case of monolayer In:SnSe/SnSe/Sb:SnSe homostructure. ACS Appl. Electron. Mater. 1, 1133–1140 (2019).
 36.
Baettig, P., Seshadri, R. & Spaldin, N. A. Antipolarity in ideal BiMnO_{3}. J. Am. Chem. Soc. 129, 9854–9855 (2007).
 37.
Goian, V. et al. Absence of ferroelectricity in BiMnO\({}_{3}\) ceramics. J. Appl. Phys. 112, 074112 (2012).
 38.
Seshadri, R. & Hill, N. A. Visualizing the role of Bi 6\(s\) “lone pairs” in the offcenter distortion in ferromagnetic BiMnO\(s\). Chem. Mater. 13, 2892–2899 (2001).
 39.
Anderson, P. W. & Blount, E. I. Symmetry considerations on martensitic transformations: “ferroelectric” metals? Phys. Rev. Lett. 14, 217 (1965).
 40.
Wojdeł, J. C. & Íñiguez, J. Testing simple predictors for the temperature of a structural phase transition. Phys. Rev. B 90, 014105 (2014).
 41.
Wang, Y., Liu, X., Burton, J. D., Jaswal, S. S. & Tsymbal, E. Y. Ferroelectric instability under screened coulomb interactions. Phys. Rev. Lett. 109, 247601 (2012).
 42.
Xia, C., Chen, Y. & Chen, H. Coexistence of polar displacements and conduction in doped ferroelectrics: an ab initio comparative study. Phys. Rev. Mater. 3, 054405 (2019).
 43.
Puggioni, D., Giovannetti, G. & Rondinelli, J. M. Polar metals as electrodes to suppress the criticalthickness limit in ferroelectric nanocapacitors. J. Appl. Phys. 124, 174102 (2018).
 44.
Puggioni, D., Giovannetti, G., Capone, M. & Rondinelli, J. M. Design of a mott multiferroic from a nonmagnetic polar metal. Phys. Rev. Lett. 115, 087202 (2015).
 45.
Zhang, Y. et al. Discovery of a magnetic conductive interface in PbZr\({}_{0.2}\)Ti\({}_{0.8}\) O\({}_{3}\) /SrTiO\({}_{3}\) heterostructures. Nat. Commun. 9, 685 (2018).
 46.
Li, M., Gu, Y., Wang, Y., Chen, L.Q. & Duan, W. Firstprinciples study of \({180}^{\circ }\) domain walls in BaTiO\({180}^{\circ }\) : Mixed BlochNéelIsing character. Phys. Rev. B 90, 054106 (2014).
 47.
Meyer, B. & Vanderbilt, D. Ab initio study of ferroelectric domain walls in PbTiO\({}_{3}\). Phys. Rev. B 65, 104111 (2002).
 48.
Henkelman, G., Uberuaga, B. P. & Jónsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901–9904 (2000).
 49.
Laidler, K. J. & King, M. C. Development of transitionstate theory. J. Phys. Chem. 87, 2657–2664 (1983).
 50.
Tadmor, E., Waghmare, U., Smith, G. & Kaxiras, E. Polarization switching in PbTiO\({}_{3}\) : an ab initio finite element simulation. Acta Mater. 50, 2989–3002 (2002).
 51.
Wang, H. & Qian, X. Twodimensional multiferroics in monolayer group IV monochalcogenides. 2D Mater. 4, 015042 (2017).
 52.
Li, X. Y. et al. Domain wall motion in perovskite ferroelectrics studied by the nudged elastic band method. J. Phys. Chem. C 122, 3091–3100 (2018).
 53.
Blöchl, P. E. Projector augmentedwave method. Phys. Rev. B 50, 17953–17979 (1994).
 54.
Kresse, G. & Furthmüller, J. Efficiency of abinitio total energy calculations for metals and semiconductors using a planewave basis set. Comp. Mater. Sci. 6, 15–50 (1996).
 55.
Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio totalenergy calculations using a planewave basis set. Phys. Rev. B 54, 11169–11186 (1996).
 56.
Perdew, J. P. et al. Restoring the densitygradient expansion for exchange in solids and surfaces. Phys. Rev. Lett. 100, 136406 (2008).
 57.
Dudarev, S. L., Botton, G. A., Savrasov, S. Y., Humphreys, C. J. & Sutton, A. P. Electronenergyloss spectra and the structural stability of nickel oxide: an LSDA.U study. Phys. Rev. B 57, 1505–1509 (1998).
 58.
Giovannetti, G. & Capone, M. Dual nature of the ferroelectric and metallic state in LiOsO\({}_{3}\). Phys. Rev. B 90, 195113 (2014).
 59.
Makov, G. & Payne, M. C. Periodic boundary conditions in ab initio calculations. Phys. Rev. B 51, 4014–4022 (1995).
 60.
Neugebauer, J. & Scheffler, M. Adsorbatesubstrate and adsorbateadsorbate interactions of Na and K adlayers on Al(111). Phys. Rev. B 46, 16067–16080 (1992).
 61.
Silvi, B. & Savin, A. Classification of chemical bonds based on topological analysis of electron localization functions. Nature 371, 683 (1994).
 62.
Ding, H.C. & Duan, C.G. Electricfield control of magnetic ordering in the tetragonallike \({{\rm{BiFeO}}}_{3}\). EPL (Europhys. Lett.) 97, 57007 (2012).
 63.
Aroyo, M. I. et al. Crystallography online: Bilbao crystallographic server. Bulg. Chem. Commun 43, 183–197 (2011).
 64.
Momma, K. & Izumi, F. VESTA 3 for threedimensional visualization of crystal, volumetric and morphology data. J. Appl. Crystallogr. 44, 1272–1276 (2011).
 65.
Togo, A. & Tanaka, I. First principles phonon calculations in materials science. Scr. Mater. 108, 1–5 (2015).
Acknowledgements
We thank Kevin Garrity, Hongjun Xiang, and T. Yamashita for valuable discussions. We acknowledge support from National Natural Science Foundation of China (No. 11774236), Pujiang Talents program (No. 17PJ1407300), the Seed Grants of NYUECNU Joint Research Institutes and the 2019 University Research Challenge Fund. This research was carried out on the High Performance Computing resources at New York University New York, Abu Dhabi and Shanghai.
Author information
Affiliations
Contributions
Y.W.F. and H.C. designed the project, performed the calculations, analyzed the results, and wrote the manuscript.
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing interests.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Rights and permissions
Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.
About this article
Cite this article
Fang, YW., Chen, H. Design of a multifunctional polar metal via firstprinciples highthroughput structure screening. Commun Mater 1, 1 (2020). https://doi.org/10.1038/s4324601900056
Received:
Accepted:
Published:
Further reading

Switching a Polar Metal via Strain Gradients
Physical Review Letters (2021)

Stressdriven grain refinement in a microstructurally stable nanocrystalline binary alloy
Scripta Materialia (2021)

Two‐Step Thermal Annealing: An Effective Route for 15 % Efficient Quasi‐2D Perovskite Solar Cells
ChemPlusChem (2021)

Investigation into CationOrdered Magnetic Polar Double Perovskite Oxides
Chemistry of Materials (2021)

Unusual magnetic transitions and phonon instabilities in tetragonal SrIrO3 under epitaxial strain
Journal of Magnetism and Magnetic Materials (2021)