Pronounced Negative Thermal Expansion in Lead-Free BiCoO3

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Pronounced Negative Thermal Expansion in Lead-Free BiCoO3Based Ferroelectrics Triggered by the Stabilized Perovskite Structure Zhao Pan, Xingxing Jiang, Takumi Nishikubo, Yuki Sakai, Hayato Ishizaki, Kengo Oka, Zheshuai Lin, and Masaki Azuma Chem. Mater., Just Accepted Manuscript • DOI: 10.1021/acs.chemmater.9b01969 • Publication Date (Web): 25 Jul 2019 Downloaded from pubs.acs.org on July 28, 2019

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Chemistry of Materials

Pronounced Negative Thermal Expansion in Lead-Free BiCoO3-Based Ferroelectrics Triggered by the Stabilized Perovskite Structure Zhao Pan,1,* Xingxing Jiang,2 Takumi Nishikubo,1 Yuki Sakai,3 Hayato Ishizaki,1 Kengo Oka,4 Zheshuai Lin,2 and Masaki Azuma1,* 1Laboratory for Materials and Structures, Tokyo Institute of Technology, 4259 Nagatsuta, Midori, Yokohama 226-8503, Japan 2Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China 3Kanagawa Institute of Industrial Science and Technology, 705-1 Shimoimaizumi, Ebina, Kanagawa 243-0435, Japan 4Department of Applied Chemistry, Faculty of Science and Engineering, Chuo University, Bunkyo, Tokyo 112-8551, Japan

ABSTRACT: Negative thermal expansion (NTE) with a giant volume shrinkage of 4.4%, comparable to the strongest NTE (V = -4.8%) in PbTiO3-based perovskites, was achieved in a lead-free BiCoO3 derivative. The giant lattice distortion of perovskite-type (ABO3) BiCoO3 (c/a = 1.27) was effectively suppressed by making solid solution with BaTiO3, which exhibits a large tolerance factor and a small lattice distortion (t = 1.06 and c/a = 1.01). As a consequence, the thermal stability of the perovskite structure of BiCoO3 was improved, and temperatureinduced polar-tetragonal to nonpolar-cubic phase transition resulting in NTE occurred. The pronounced NTE is attributed to the weakened ferroelectricity caused by hybridization between the A/B-site cations and oxygen, as evidenced by comprehensive experimental and theoretical investigations. The present study of tuning the tolerance factor provides guidelines for realizing large NTE in lead-free compounds with a large structure distortion.

INTRODUCTION Negative thermal expansion (NTE) is an intriguing phenomenon whereby the volume shrinks rather than expands with increasing temperature. The discovery of NTE provides an opportunity to control the overall thermal expansion of structural materials.1-3 The last few decades have witnessed great progress on NTE materials. In particular, certain materials have shown NTE coupled with phase transitions, such as the metal-insulator transition in ruthenates,4 the magnetovolumetric effect in Invar alloys and manganese nitrides,5,6 intermetallic charge transfer in LaCu3Fe4O12 and BiNiO3,7,8 and ferroelectrostriction in PbTiO3based ferroelectrics.2,9 The NTE associated with the phase transitions in these functional materials usually occurs in a narrow temperature range; the volume shrinkage is much more remarkable than in other NTE materials. The magnitude of the shrinkage is an important factor since the working temperature range and the coefficient of thermal expansion (CTE) are generally in a trade-off relation.8,10 Such phase-transition-type NTE materials are of great significance from the perspectives of both fundamental research and practical applications. Among phase-transition-type NTE materials, the perovskitetype (ABO3) ferroelectric PbTiO3 with a large tetragonal distortion (c/a = 1.06) and spontaneous polarization (PS = 59 μC/cm2) exhibits unusual NTE in a wide temperature range from room temperature to its Curie temperature (TC = 763 K), with an average volumetric CTE of -1.9910-6/K.11 NTE in PbTiO3 and its derivatives has been well studied.2 The origin is attributed to the structural transition from polar-tetragonal to nonpolar-cubic phases during heating.2,12 NTE in the PbTiO3 family mainly depends on shrinkage of the polar c-axis in the tetragonal phase;

therefore, it is expected that an increase in the c/a ratio will lead to a larger NTE. Indeed, a large NTE with V = -4.8% was recently reported in 0.5PbTiO3-0.5BiCoO3 (c/a = 1.17) by improving the tetragonality of PbTiO3.13 Note that BiCoO3 is isostructural with PbTiO3, but its lattice distortion (c/a = 1.27) and polarization (PS = 131 μC/cm2), calculated using the point charge model, are more pronounced.13-15 Intriguingly, BiCoO3 exhibits a large pressureinduced volume shrinkage of 13% during the phase transition,15 which suggests it promising as a large lead-free NTE material. However, such a large structural distortion makes its decomposition temperature (Td) as low as 720 K, which hinders observation of a temperature-induced tetragonal-to-cubic (T-C) phase transition resulting in NTE.14 Attempts have been made to reduce the lattice distortion in BiCoO3, such as by making solid BiCo1-xFexO3, and solutions of Bi1-xLaxCoO3, Bi0.9Sm0.1Co1-xFexO3,16,17 in order to realize lead-free NTE ferroelectrics. However, these efforts hardly decreased the lattice distortion in the tetragonal phase, and the compounds generally decomposed before reaching the phase transition temperature. Thus, observation of NTE in those tetragonal perovskites with strong polarity remains a challenge. Electron doping was recently found to effectively reduce the c/a ratio and induce NTE in PbVO3 with similar giant tetragonal structure (c/a = 1.23).18,19 However, our attempts to induce NTE by electron doping in BiCoO3 were not successful. One possible reason is the small tolerance factor (t) of BiCoO3 (t = 0.90) arising from Bi3+Co3+ charge combination.20 Tetragonal P4mm structure generally appears for t > 1, but small t also stabilizes largely distorted polar LiNbO3 (t = 0.86) type structure.21 It is therefore expected that substitution of large (small) divalent (tetravalent)

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cation into Bi3+ (Co3+) site reduces the c/a ratio of BiCoO3 and enables the structural transition. Herein, we achieved both composition- and temperature-induced tetragonal-to-cubic phase transitions in lead-free BiCoO3 by making solid solution with the less distorted Ba2+Ti4+O3 (c/a = 1.01, t = 1.06).22 We found that BaTiO3 substitution effectively suppresses the tetragonal distortion of BiCoO3 and stabilizes the perovskite structure at high temperature. Accordingly, a temperature-induced T-C phase transition occurs accompanied by a maximum volume shrinkage of 4.4%, as shown by comprehensive experimental and theoretical studies. EXPERIMENTAL METHODS Samples of (1-x)BiCoO3-xBaTiO3 (abbreviated as (1-x)BCxBT, x = 0.0 - 0.50) were prepared with a cubic anvil-type highpressure apparatus. The stoichiometric powder mixture of Bi2O3, Co3O4, BaO, and TiO2 was sealed in a platinum capsule and was reacted at 6 GPa and 1473 K for 30 min. 10 mg of KClO4 oxidizing agent (approximately 10 wt% of the sample) was separately added to the top and bottom of the capsule. After heat treatment, the samples were quenched to room temperature (RT), and the pressure was slowly released. The obtained samples were crushed and washed with distilled water to remove the remaining KCl, and then annealed at 673 K for 4 h in order to remove the residual stress during the high-pressure process. Powder X-ray diffraction (XRD) data were collected with a diffractometer using Cu K radiation (D8 ADVANCE, Brucker). The synchrotron X-ray diffraction (SXRD) patterns were collected at the BL02B2 ( = 0.421026 Å) and BL19B2 ( = 0.420105 Å) beam lines of SPring-8 and the 11ID-C ( = 0.117420 Å) beam line of the Advanced Photon Source. The detailed crystal structure was refined using the full-profile Rietveld method in the FullProf software.

resulted in the reduction of tetragonal distortion and finally to the transition to cubic as we expected. The precise structural parameters for the selected tetragonal (x = 0.20), coexisting tetragonal and cubic (x = 0.31), and single cubic (x = 0.40) compounds were refined using the SXRD data and are listed in the Supporting Information (Figure S1-S3 and Table S1). As expected, the c/a ratio shows a significant decreasing tendency from 1.27 for pure BiCoO3 to 1.15 for 0.7BC-0.3BT, and unity for the cubic phase, as shown in Figure 1b. Correspondingly, the polyhedral gradually changes from a large distorted BO5 pyramidal coordination to a regular BO6 octahedral one (see the inset of Figure 1b). The reduced tetragonality in (1-x)BC-xBT is attributed to suppressed spontaneous polarization (PS) due to the weakened hybridization between A/B site cations and oxygen.12 Here, PS gradually decreases as a result of the chemical substitution with BaTiO3; PS is 131 μC/cm2 for undoped BiCoO3, and 119, 104, and 97μC/cm2 for 0.9BC-0.1BT, 0.8BC-0.2BT, and 0.7BC-0.3BT, respectively. Note that the present composition-induced T-C phase transition is rarely observed in such strong polar perovskites. Indeed, much effort has been put into strong polar perovskites, such as PbVO3 (c/a = 1.23),30 Bi(Zn0.5Ti0.5)O3 (c/a = 1.21),31 and BiCoO3, in order to reduce their large lattice distortion and thereby study their ferroelectric and thermal expansion properties. However, almost all of the attempts, except for certain PbVO3 derivatives,18,32 have resulted in a tetragonal to monoclinic phase transition rather than the T-C one, or have decomposed before reaching the transition temperature.16,33,34

The first-principles electronic density calculations of BiCoO3, 0.8BiCoO3-0.2BaTiO3, and 0.5BiCoO3-0.5BaTiO3 were performed with CASTEP, a plane-wave pseudopotential total energy package based on density functional theory (DFT).23 The exchangecorrelation items in the Hamiltonian were modelled using functionals developed by Perdew, Burke, and Ernzerhof (PBE)24 in the generalized density approximation (GGA)25 form. Adoption of an optimized norm-conserving pseudopential26 in the KleimanBylander27 form allowed us to use a small plane basis set without compromising the accuracy required for the calculation. A kinetic energy cutoff of 900 eV and Monkhorst-pack28 k-point mesh spanning less than 0.03 Å-1 in the Brillouin zone were chosen. The virtual crystal approximation (VCA) algorithim29 was used to treat the Bi/Ba and Co/Ti disorder, in which the effective interaction between the disordered site and the valence electrons was set to the weighted sum based on its element constitution. RESULTS AND DISCUSSION The XRD patterns of (1-x)BC-xBT are shown in Figure 1a. It can be seen that all the samples have a pure perovskite structure. Samples of x  0.30 exhibit tetragonal phase, however, the separation between the (001) and (100) peaks decreases as the amount of substituted BaTiO3 increases, indicating a decrease in the c/a ratio. Notably, the tetragonal and cubic phases coexist in the range of 0.30 < x  0.35, and the cubic phase progressively increases in this composition range. Eventually, a compositioninduced single cubic phase appears at x  0.40. The increase in t

Figure 1. (a) XRD patterns and (b) composition dependence of the c/a ratio of (1-x)BC-xBT (x = 0.0 - 0.50). The inset indicates the transformation from a pyramidal BO5 coordination to a BO6 octahedral one.


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Chemistry of Materials The decreased c/a ratio in BiCoO3 provides an opportunity to investigate its thermal expansion properties. The temperature variation of the SXRD data was estimated for the (1-x)BC-xBT (x = 0.30, 0.31, 0.32, and 0.35) samples. BaTiO3 substitution significantly improved the thermal stability of the perovskite structure. For the 0.70BC-0.30BC compound, Td increased to ~900 K (Figure S4), which is in sharp contrast to that of BiCoO3 (Td = 720 K).14 In addition, the cubic phase appeared at 773 K, indicating the T-C phase transition. Unfortunately, the 0.70BC0.30BC compound decomposed before it had completely changed to the cubic phase. However, 0.69BC-0.31BT showed a clear phase transition with more BaTiO3. As depicted in Figure 2a, both the tetragonal and cubic phase coexisted below 730 K, and the (001) and (100) peaks for the tetragonal phase merged into a single (100) one at 780 K, indicating a complete structural transition. The 0.69BC-0.31BC compound decomposed above 880 K. A similar phase transition was observed in the 0.68BC-0.32BC and 0.65BC0.35BC samples (Figure S5 and S6). Even though the separation between the (001) and (100) peaks did not show a noticeable change, the intensity ratio of the cubic and tetragonal phases increased during the heating, which indicates an increase in the fraction of the cubic phase. Note that this is the first report of such a temperature-induced cubic phase in BiCoO3 end-member perovskites. Previous attempts at creating a T-C phase transition in BiCoO3, such as with BiCo1-xFexO3, failed due to poor thermal stability.17

On the basis of the high-temperature SXRD results, we constructed a composition versus temperature phase diagram (Figure 2b). BaTiO3 substitution improves the thermal stability of BiCoO3 and stabilizes its perovskite structure at high temperature. The samples with a small amount of BaTiO3 (x  0.30) maintain a tetragonal phase and decompose before reaching the transition temperature. For compounds with 0.30 < x  0.35, the tetragonal and cubic phases coexist at room temperature and transform into a single cubic phase at TC. TC slightly decreases with increasing BaTiO3, and the samples decompose at a certain temperature above their TC. Increasing the content of BaTiO3 even more (x  0.40) leads to stabilization of the cubic phase at room temperature.

Figure 3. Temperature dependence of refined lattice parameters and fraction of cubic phase for (a) 0.69BC-0.31BT, (b) 0.68BC-0.32BT, and (c) 0.65BC-0.35BT. (d-f) The corresponding weighted average unit cell volumes as a function of temperature. The volume shrinkage (V) within the NTE temperature range and a schematic illustration of the SVFS (ωS) are also shown in each panel.

Figure 2. (a) Temperature dependence of SXRD of 0.69BC-0.31BT indicating a mixed tetragonal and cubic to single cubic phase transition on heating. The diamond indicates the secondary phase. (b) Composition-temperature phase diagram for the (1-x)BC-xBT system. Both the tetragonal and cubic phase coexist at the data points represented by the crosses.

Figures 3a, b, and c show the temperature dependence of the lattice parameters and fraction of cubic phase of samples with x = 0.31, 0.32, and 0.35. The lattice parameters of each phase exhibit a slight increase before the phase transition, followed by a large shrinkage of the c-axis (i.e., 10% for 0.69BC-0.31BT) on approaching TC, while the a-axis expands only by 3%. As a result, shrinkage in the unit cell volume, i.e., NTE, occurs as the amount of cubic phase increases. Using the lattice parameters and the phase fractions, the weighted average unit cell volumes were calculated (Figures 3d, e, and f). Large volume shrinkages of 4.4% (625 - 780 K), 3.4% (600 - 800 K), and 1.9% (600 - 750 K) were calculated for x = 0.31, 0.32, and 0.35, respectively. Here, the maximum volume shrinkage, 4.4%, is larger than in most of the representative large NTE materials, including the framework structure ZrW2O8 (-1.2%, T < 425 K),35 Bi0.95La0.05NiO3 (-2.0%, 320 - 380 K) and 0.5PbTiO30.5BiFeO3 (-2.1%, 573 - 873 K) perovskites,8,9 and Mn3Co0.98Cr0.02Ge (-3.2%, 122 - 322 K) antiperovskite.36 It is even comparable to that of 0.5PbTiO3-0.5BiCoO3 (-4.8%, 948 - 973 K), which was recently reported to exhibit the strongest NTE in



PbTiO3-based NTE materials.13 Note that the present NTE material has the advantage of being lead-free. Experimental and theoretical studies suggest that ferroelectricity plays a critical role in the NTE of perovskite ferroelectrics.2,37 In the ferroelectric phase, an increase in volume can be maintained by the large c/a resulting from the strong PS, while PS and NTE disappears in the paraelectric phase above TC.38 A new concept of spontaneous volume ferroelectrostriction (SVFS, ωS) has been proposed for ferroelectric materials as a way to quantitatively evaluate the contribution of ferroelectricity to NTE.9 A large ωS generally indicates a large contribution of ferroelectricity to the volume enhancement. The SVFS is defined as follows,

ωS 

V nm - V exp V nm

 100% ,

where Vexp and Vnm represent the experimental and nominal unit cell volumes, respectively. Vnm can basically be estimated by extrapolation from the paraelectric to ferroelectric phase. Here, the ωS values for x = 0.31, 0.32 and 0.35 are 7.4%, 6.9%, and 1.9%, respectively. It should be noted that the present ωS values may have been overestimated since the temperature range corresponding to the cubic phase is only within 100 K, which will lead to a somewhat ambiguous estimation of Vnm. In comparison, the ωS value of 0.69BC-0.31BT is larger than that of typical PbTiO3-based NTE materials such as PbTiO3 (3.1%) and 0.5PbTiO3-0.5BiFeO3 (5.0%).2,9 The larger ωS indicates a stronger ferroelectrovolume effect, which is consistent with a larger volume shrinkage during the ferroelectric to paraelectric phase transition.

manifests strong orbital hybridization during formation of the CoO5 pyramid. On the other hand, in 0.8BT-0.2BT, the anisotropy of the electronic cloud redistribution is smaller (Figure 4b), and the corresponding area eventually changes into a nearly spherical one in cubic 0.5BC-0.5BT (Figure 4c). This indicates that the orbital hybridization is blunted by the Co/Ti substitution. As for the electrons in BiCoO3 (Figure 4d), a large electron-gaining area concentrates around the Bi-O bond, implying strong covalency. However, in 0.8BC-0.2BT, the electron-gaining area around the Bi0.8Ba0.2-O bonds is reduced (Figure 4e), while in 0.5BC-0.5BT, strong ionicity dominates the Bi0.5Ba0.5-O bond (Figure 4f), implying that Bi/Ba substitution also reduces the covalency of the Bi/Ba-O bond. Therefore, the decrease in ferroelectricity from BiCoO3, from 0.8BC-0.2BT to 0.5BC-0.5BT, can be attributed to the reduced orbital hybridization due to Bi/Ba and Co/Ti substitution, which corresponds well with the weakened PS and suppressed c/a. The present study not only extends the scope of NTE families, but also lights a way to realize NTE in lead-free polar perovskites, such as Bi(Zn0.5Ti0.5)O3 and Bi(Zn0.5V0.5)O3. PbTiO3 exhibits unusual NTE during the ferroelectric to paraelectric phase transition.11 Polar perovskites such as PbVO3 (c/a = 1.23),30 Bi(Zn0.5Ti0.5)O3 (c/a = 1.21),31 Bi(Zn0.5V0.5)O3 (c/a = 1.26),39 and BiCoO3 (c/a = 1.27)14 are isostructural with PbTiO3 (c/a = 1.06), but the tetragonalities are more pronounced. Therefore, large NTE is expected in those tetragonal perovskites. Indeed, giant NTE was achieved in PbVO3 derivatives by suppressing the tetragonal distortion.10,18,19,40 Here the present results indicate that the tetragonal phase can be destabilized by tuning the tolerance factor through making solid solution with less distorted compound with a large tolerance factor, e.g., BaTiO3. Other unreported solid solutions that contain polar perovskites such as Bi(Zn0.5Ti0.5)O3 and Bi(Zn0.5V0.5)O3 should also exhibit the composition- and temperature-induced tetragonal to cubic phase transition accompanied by NTE, as observed in the present (1-x)BiCoO3xBaTiO3 system. In addition, such materials design to control the degree of tetragonal distortion can be utilized for lead-free ferroelectric/piezoelectric materials since those giant tetragonal perovskites can be regarded as promising parent compounds. CONCLUSIONS

Figure 4. Electron density difference map around Co(Ti)-O bond in (a) BiCoO3, (b) 0.8BiCoO3-0.2BaTiO3, and (c) 0.5BiCoO30.5BaTiO3 and Bi(Ba)-O bond in (d) BiCoO3, (e) 0.8BiCoO30.2BaTiO3, and (f) 0.5BiCoO3-0.5BaTiO3. Bi(Ba), Co(Ti), and O atoms are represented by blue, green and red balls, respectively.

In perovskite ferroelectrics, hybridizations between A/B-site cations and oxygen are essential for the polar distortion.12 To further study the effect of BaTiO3 substitution on ferroelectricity and thereby study how it affects the NTE, a first-principles calculation of the electronic density difference distribution was conducted (Figure 4). Accordingly, in the pristine BiCoO3, electrons are transferred from cobalt to oxygen atoms, and redistribution of the electronic cloud around the Co-O bonds exhibits a prominent spatial orientation (Figure 4a), which

In summary, both composition- and temperature-induced tetragonal to cubic phase transitions were successfully achieved in lead-free BiCoO3 derivative ferroelectrics by tailoring the tolerance factor through making solid solutions with BaTiO3. The less distorted BaTiO3 with a large tolerance factor effectively suppressed the giant lattice distortion of BiCoO3 and improved the thermal stability of its perovskite structure. As expected, the composition of 0.69BC-0.31BT exhibited a volume shrinkage as large as 4.4%, which is comparable to that of the strongest NTE in lead-based ferroelectrics. The present study provides an effective way to realize NTE in lead-free polar perovskites, and extends the scope of NTE in ferroelectrics.

ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website. Details of the Rietveld refinements (x = 0.2, 0.31, and 0.35) and the


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Chemistry of Materials high-temperature SXRD patterns (x = 0.30, 0.31, and 0.35) for (1x)BC-xBT.

AUTHOR INFORMATION Corresponding Authors *E-mail: [email protected] (Z.P.). *E-mail: [email protected] (M.A).

Notes The authors declare no competing financial interests.

ACKNOWLEDGMENT This work was partially supported by Grants-in-Aid for Scientific Research 16H02393 and 18H05208 from the Japan Society for the Promotion of Science (JSPS), the National Natural Science Foundation of China (21805215), and the World Research Hub Initiative (WRHI) of Tokyo Institute of Technology. The synchrotron radiation experiments were performed at SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (2018B1222, 2018B1860, and 2019A1045). The use of the Advanced Photon Source at Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Science (DE-AC02-06CH11357).

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Pronounced Negative Thermal Expansion in Lead-Free BiCoO3

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