Research

IRG 1 - Designing Functionality into Layered Ferroics

Description

IRG1, Designing Functionality into Layered Ferroics, will showcase materials discovery by design for electric field control of electronic, optical, magnetic and structural response of materials starting from the level of atoms. The goal is to design and discover fundamental new mechanisms and material classes of acentric layered oxides with strong coupling to spin, charge, and lattice degrees of freedom. An unprecedented expansion of ferroic families in layered oxides – a vast and largely unexplored materials class with unique control knobs in chemistry, topology, and geometry – will enable the design of ferro- & ferri-electricity, magnetoelectricity, multiferroicity, and gradient-driven effects. We will counterpoise competing phases with colossal properties to transform otherwise nonpolar materials into strongly polar ones and will couple electrical, magnetic and structural order parameters. Group theory, materials informatics, first-principles DFT, model Hamiltonians, and phase-field modeling will predict new ferroic systems and guide experimental efforts. Potential new technologies include room temperature electric field control of ferromagnetism, highly nonlinear optical materials, high temperature piezoelectrics, GHz electronics, and electric field control of correlated phenomena.

Past highlights:

• Discovery of new metastable phase with large property enhancements. (Nature Commun., 2014)¹
• Discovery of a new family of improper acentric layered oxides, NaRETiO₄, through oxygen octahedral rotations (Phys. Rev. Lett., 2014)²
• Prediction and discovery of a Ruddlesden-Popper layered ferroic with the highest figure of merit for dielectric tuning ever reported. (Nature, 2013) ³
• Of the six main mechanisms for multiferroics today, four were discovered by our team: Spin-phonon coupling, A-site ferroelectricity/B-site magnetism, Coupled JT and DM interactions, and Hybrid improper multiferroics.⁴
• Octahedral rotations in layered perovskites exhibit new symmetries and "roto" properties (Nature Materials, 2011,⁵ Phys. Rev. B, 2012⁶) such as mediating coupling between polarization and magnetism in layered perovskites (Phys. Rev. Lett., 2011⁷) , and with strain (Phys. Rev. B, 2011⁸).
• A paraelectric antiferromagnet in bulk form such as EuTiO₃, when biaxially strained in thin film form becomes a strong ferroelectric ferromagnet (Nature, 2010,⁹ 2011¹⁰). Electrical control of magnetism is demonstrated (Nature Comm. 2013¹¹).
• New insights into the atomic scale structure and dynamics of ferroelectric domain walls, such as Bloch and Neel-like ferroelectric walls (Phys. Rev. B, 2009¹²) long-range influence (Phys. Rev. B, 2010¹³), atomic resolution dynamics (Science, 2011,¹⁴ Nature Commmun. 2011¹⁵), and wall properties (Phys. Rev. Lett., 2012,¹⁶ Phys. Rev. B, 2012¹⁷).
• Strain-induced isosymmetric phase transitions (Science, 2009,¹⁸ Phys. Rev. Lett., 2013,¹⁹) domain walls (Phys. Rev. Lett., 2013²⁰), large nonlinear optical coefficients (Appl. Phys. Lett., 2013²¹), and observation of room temperature magnon sidebands (Phys. Rev. B, 2009 ²²) in BiFeO₃.
• Ferroelectricity in strained SrTiO₃ (Phys. Rev. Lett. 2010,²³ Science, 2009,²⁴ Phys. Rev. Lett., 2008²⁵) and CaTiO3 (Phys. Rev. B, 2009²⁶).
• Multiphase multiferroics and devices (Advanced Materials, 2012,^27,28 Nature Commun. 2011^29,30Appl. Phys. Lett. 2011,³¹ Phys. Rev. Lett. 2010. ³²)

References:

(1) T. T.A. Lummen, Yijia Gu, Jianjun Wang, Shiming Lei, Amit Kumar, Andrew T. Barnes, Eftihia Barnes, Sava Denev, Alex Belianinov, Martin Holt, Anna N. Morozovska, Sergei V. Kalinin, Long-Qing Chen and Venkatraman Gopalan, “Thermotropic phase boundaries in classic ferroelectrics,” Nat. Commun. 5, 3172 (2014).

(2) H. Akamatsu, K. Fujita, T. Kuge, A. S. Gupta, A. Togo, S. Lei, F. Xue, G. Stone, J. M. Rondinelli, L. Q. Chen, I. Tanaka, V. Gopalan, K. Tanaka, “Inversion symmetry breaking by oxygen octahedral rotations in Ruddlesden-Popper NaRETiO₄ family” Phys. Rev. Lett. 112, 187602 (2014).

(3) C-H.Lee, N. D. Orloff, T. Birol, Y. Zhu, V. Goian, R. Haislmaier, E. Vlahos, J. A. Mundy, Y. Nie, M. D. Biegalski, J. Zhang, M. Bernhagen, N. A. Benedek, Y. Kim, J. D. Brock, R. Uecker, X. Xi, V. Gopalan, D. Nuzhnyy, S. Kamba, D. A. Muller, I. Takeuchi, J. C. Booth, C. J. Fennie & D. G. Schlom, "Exploiting Dimensionality and Defect Mitigation to Create Tunable Microwave Dielectrics," Nature, doi:10.1038/nature12582 (published on-line on October 16, 2013) (2013).

(4) The six main mechanisms are: (a) Spin spirals and exchange-striction: T. Kimura, "Spiral Magnets as Magnetoelectrics", Annu. Rev. Mater. Res. 37, 387-413 (2007); I. Sergienko, C. Sen, and E. Dagotto, "Ferroelectricity in the Magnetic E-Phase of Orthorhombic Perovskites", Phys. Rev. Lett. 97, 227204 (2006); (b) Charge ordered multiferroics: N. Ikeda, H. Ohsumi, K. Ohwada, K. Ishii, T. Inami, K. Karurai, Y. Murakami, K. Yoshii, S. Mori, Y. Horibe, and H. Kito, "Ferroelectricity from iron valence ordering in the charge-frustrated system LuFe₂O₄", Nature 436, 1136 (2005); H. J. Xiang, M.-H.Whangbo, "Charge ordering and the origin of giant magnetocapacitance in LuFe₂O₄", Phys. Rev. Lett. 98, 246403 (2007); (c) Spin-phonon coupling: C. J. Fennie and K. M. Rabe, "Magnetic and electric phase control in epitaxial EuTiO₃ from first principles", Phys. Rev. Lett. 97 267602 (2007); J. H. Lee, L. Fang, E. Vlahos, X. Ke, Y. W. Jung, L. Fitting Kourkoutis, J.-W. Kim, P. J. Ryan, T. Heeg, M. Roeckerath, V. Goian, M. Bernhagen, R. Uecker, P. C. Hammel, K. M. Rabe, S. Kamba, J. Schubert, J. W. Freeland, D. A. Muller, C. J. Fennie, P. Schiffer, V. Gopalan, E. Johnston-Halperin, and D. G. Schlom, "A Strong Ferroelectric Ferromagnet Created by means of Spin-Lattice Coupling", Nature 466, 954 (2010); (d) A-site ferroelectricity, B-site magnetism: N. A. Hill (Spaldin), "Why are there so few magnetic ferroelectrics", J. Phys. Chem. B 104, 6694 (2000); J. Wang, J. B. Neaton, H. Zheng, V. Nagaraj, S. B. Ogale, B. Liu, D. Viehland, V. Vaidyanathan, D. G. Schlom, U. V. Waghmare, N. A. Spaldin, K. M. Rabe, M. Wuttig, and R. Ramesh, "Epitaxial BiFeO₃ multiferroic thin film heterostructures", Science 299, 1719 (2003); (e) Coupled JT and DM interactions: C. J. Fennie, "Ferroelectrically induced weak-ferromagnetism by design", Phys. Rev. Lett. 100, 167203 (2008); (f) Hybrid Improper Multiferroics: N. A. Benedek and C. J. Fennie, "Hybrid Improper Ferroelectricity: A Mechanism for Controllable Polarization-Magnetization Coupling", Phys. Rev. Lett. 106, 107204 (2011).

(5) V. Gopalan, D. B. Litvin, "Rotation-reversal symmetries in crystals and handed structures," Nature Materials, 10, 376 (2011).

(6) A. N. Morozovska, E. A. Eliseev, M. D. Glinchuk, V. Gopalan, "Interfacial Polarization and pyroelectricity in antiferrodistortive structures induced by a flexoelectric effect and rotostriction," Phys. Rev. B, 85, 094107 (2012).

(7) T. Birol, N. A. Benedek, C. J. Fennie, "Interface control of emergent ferroic order in Ruddlesden-Popper Sr_n+1Ti_nO_3n+1," Phys. Rev. Lett., 107, 257602 (2011).

(8) R. L. Johnson-Wilke, D. S. Tinberg, C. B. Yeager, Y. Han, I. M. Reaney, I. Levin, D. D. Fong, T. T. Fister, S. Trolier-Mckinstry, "Tilt transitions in compressively strained AgTa_0.5Nb_0.5O₃ thin films," Phys. Rev. B, 84, 134114 (2011).

(9) J.H. Lee, L. Fang, E. Vlahos, X. Ke, Y.W. Jung, L. Fitting Kourkoutis, J-W. Kim, P.J. Ryan, T. Heeg, M. Roeckerath, V. Goian, M. Bernhagen, R. Uecker, P.C. Hammel, K.M. Rabe, S. Kamba, J. Schubert, J.W. Freeland, D.A. Muller, C.J. Fennie, P. Schiffer, V. Gopalan, E. Johnston-Halperin, and D.G. Schlom, "A Strong Ferroelectric Ferromagnet Created by means of Spin-Lattice Coupling," Nature 466 (2010) 954-958.

(10) J.H. Lee, L. Fang, E. Vlahos, X. Ke, Y.W. Jung, L. Fitting Kourkoutis, J-W. Kim, P.J. Ryan, T. Heeg, M. Roeckerath, V. Goian, M. Bernhagen, R. Uecker, P.C. Hammel, K.M. Rabe, S. Kamba, J. Schubert, J.W. Freeland, D.A. Muller, C.J. Fennie, P. Schiffer, V. Gopalan, E. Johnston-Halperin, and D.G. Schlom, "A Strong Ferroelectric Ferromagnet Created by means of Spin-Lattice Coupling," Nature 466 (2010) 954-958.

(11) P.J. Ryan, J.-W. Kim, T. Birol, P. Thompson, J.-H. Lee, X. Ke, P.S. Normile, E. Karapetrova, P. Schiffer, S.D. Brown, C.J. Fennie, D.G. Schlom, "Reversible control of magnetic interactions by electric field in a single-phase material," Nature Communications, 4, DOI: 10.1038/ncomms2329, January (2013).

(12) Donghwa Lee Rakesh K. Behera, Pingping Wu, Haixuan Xu, Y. L. Li, Simon R. Phillpot, Susan B. Sinnott, L. Q. Chen, V. Gopalan, "Mixed Bloch-Neel-Ising Character of 180 Degree Ferroelectric Domain Walls," Phys. Rev. B. Rapid Communications, 80, 060102(R)(2009).

(13) A. Vasudevarao, A. N. Morozovska, I. Grinberg, S. Bhattacharya, Y. Li, S. Jesse, P. Wu, K. Seal, S. Choudhury, E.A. Eliseev, S. Svechnikov, D. Lee, S. Phillpot, L.Q. Chen, A. M. Rappe, V. Gopalan and S.V. Kalinin, "Correlated polarization switching in the proximity of a 180 degree domain wall," Phys. Rev. B. 82, 024111 (2010).

(14) C. T. Nelson, P. Gao, J. R. Jokisaari, C. Heikes, C. Adamo, A. Melville, S-H. Baek, C. M. Folkman, B. Winchester, Y. Gu, Y. Liu, K. Zhang, E. Wang, J. Li, L-Q. Chen, C-B. Eom, D. G. Schlom, X. Pan, "Domain dynamics during ferroelectric switching," Science, 334, 968-971 (2011).

(15) P. Gao, C. T. Nelson, J. R. Jokisaari, S-H. Baek, C. W. Bark, Y. Zhang, E. Wang, D. G. Schlom, C-B. Eom, X. Pan, "Revealing the role of defects in ferroelectric switching with atomic resolution," Nature Commun. 2, article number 591, doi: 110.1038/ ncomms 1600. (2011)

(16) Q. He, C.-H. Yeh, J.-C. Yang, G. Singh-Bhalla, C.-W. Liang, P.-W. Chiu, G. Catalan, L.W. Martin, Y.-H. Chu, J. F. Scott, and R. Ramesh, "Magnetotransport at domain walls in BiFeO₃," Phys. Rev. Lett. 108, 067203 (2012).

(17)E. A. Eliseev, A. N. Morozovska, Y. Gu, A. Borisevich, L-Q. Chen, V. Gopalan, S. V. Kalinin, "Conductivity of twin walls-surface junctions in ferroelastics-Interplay of deformation potential, octahedral rotations, improper ferroelectricity, and flexoelectric coupling," Phys. Rev. B. 86, 085416 (2012).

(18) R.J. Zeches, M.D. Rossell, J.X. Zhang, A.J. Hatt, Q. He, C.-H. Yang, A. Kumar, C.H. Wang, A. Melville, C. Adamo, G. Sheng, Y.-H. Chu, J.F. Ihlefeld, R. Erni, C. Ederer, V. Gopalan, L.Q. Chen, D.G. Schlom, N.A. Spaldin, L.W. Martin, and R. Ramesh, "A Strain-Driven Morphotropic Phase Boundary in BiFeO₃," Science 326, 977 (2009).

(19)J. C. Yang, Q. He, S. J. Suresha, C. Y. Kuo, R. Haislmaier, G. Sheng, C. Adamo, H. J. Liu, C. W. Liang, C. Y. Peng, H. J. Lin, Z. Hu, L. Chang, C. T. Chen, L. H. Tjeng, E. Arenholz, D. G. Schlom, V. Gopalan, L. Q. Chen, Y. H. Chu, and R. Ramesh, "Orthorhombic BiFeO₃ Multiferroic Thin Films," Phys. Rev. Lett., 109, 247606 (2012).

(20) Y. Wang, C. Nelson, A. Melville, B. Winchester, S. L. Z. K. Liu, D. G. Schlom, X. Q. Pan, L.-Q. Chen. " BiFeO3 Domain Wall Energies and Structures: A Combined Experimental and Density Functional Theory plus U Study," Phys. Rev. Lett. 110, 267601 (2013).

(21) R. C. Haislmaier, N. J. Podraza, S. Denev, A. Melville, D. G. Schlom, V. Gopalan, "Large nonlinear optical coefficients in pseudo-tetragonal BiFeO3 thin films," Appl. Phys. Lett. 103, 031906 (2013).

(22) M. O. Ramirez, A. Kumar, S. Denev, N. Podraza, X. S. Xu, R. C. Rai, Y. H. Chu, J. Seidel, L. Martin, S-Y. Yang, E. Saiz, J. F. Ihlefeld, S. Lee, S. W. Cheong, D. G. Schlom, R. Ramesh, J. Orenstein, J. L. Musfeldt, and V. Gopalan, "Magnon Sidebands in Bismuth Ferrite Probed by Nonlinear Optical Spectroscopy," Phys. Rev. B. 76, 224106 (2009).

(23) H. W. Jang, A. Kumar, S. Denev, M. D. Biegalski, P. Maksymovych, C. T. Nelson, C. M. Folkman, S. H. Baek, N. Balke, D. G. Schlom, L. Q. Chen, X. Q. Pan, S. V. Kalinin, V. Gopalan, and C. B. Eom, "Ferroelectricity in strain-free SrTiO₃ films," Phys. Rev. Lett. 104, 197601(2010).

(24) M.P. Warusawithana, C. Cen, C.R. Sleasman, J.C. Woicik, Y.L. Li, L. Fitting Kourkoutis, J.A. Klug, H. Li, P. Ryan, L-P. Wang, M. Bedzyk, D.A. Muller, L.Q. Chen, J. Levy, and D.G. Schlom, "A Ferroelectric Oxide Made Directly on Silicon," Science 324 (2009) 367-370.

(25) S. Denev, A. Kumar, M. Biegalski, H. W. Wang, C. M. Folkman, A. Vasudevarao, Y. Han, I. M. Reaney, S. T. Mckinstry, C. B.- Eom, D. G. Schlom, V. Gopalan, "Magnetic color symmetry of lattice rotations in a diamagnetic material," Phys. Rev. Lett., 100, 257601-1/4 (2008).

(26) C.-J. Eklund, C. J. Fennie, and K. M. Rabe, "Strain-induced ferroelectricity in orthorhombic CaTiO₃ from first principles," Phys. Rev. B 79, 220101 (2009).

(27) J. M. Hu, Z. Li, L. Q. Chen, C. W. Nan, "Design of a voltage-controlled magnetic random access memory based on anisotropic magnetoresistance in a single magnetic layer," Advanced Materials, 24, 2869-2873 (2012).

(28) P. Gao, C. T. Nelson, J. R. Jokisaari, Y. Zhang, S. H. Baek, C. W. Bark, E. Wang, Y. M. Liu, J. Y. Li, C. B. Eom, X. Q. Pan, "Direct observations of retention failure in ferroelectric memories," Advanced Materials, 24, 1106-1110 (2012).

(29) Q. He, Y.-H. Chu, J. T. Heron, S. Y. Yang, W. I. Liang, C. Y. Kuo, H. J. Lin, P. Yu, C. W. Liang, R. J. Zeches, W. C. Kuo, J. Y. Juang, C. T. Chen, E. Arenholz, A. Scholl, R. Ramesh, "Electrically controllable spontaneous magnetism in nanoscale mixed phase multiferroics," Nature Commun. 2, 225 (2011).

(30) J.M. Hu, Z. L. Q. Chen, C. W. Nan, "High-density magnetoresistive random access memory operating at ultralow voltage at room temperature," Nature Commun. 2, 553 (2011).

(31) Q. He, Y.-H. Chu, J. T. Heron, S. Y. Yang, W. I. Liang, C. Y. Kuo, H. J. Lin, P. Yu, C. W. Liang, R. J. Zeches, W. C. Kuo, J. Y. Juang, C. T. Chen, E. Arenholz, A. Scholl, R. Ramesh, "Electrically controllable spontaneous magnetism in nanoscale mixed phase multiferroics," Nature Commun. 2, 225 (2011).

(32) L. Palova, P. Chandra, K.M. Rabe, "Magnetostructural Effect in the multiferroic BiFeO₃-BiMnO₃ checkerboard from first principles," Phys. Rev. Lett. 104, 037202 (2010).