Switchable electric polarization and ferroelectric domains in a metal-organic-framework
Source abstract
Abstract
Abstract Multiferroics and magnetoelectrics with coexisting and coupled multiple ferroic orders are materials promising new technological advances. While most studies have focused on single-phase or heterostructures of inorganic materials, a new class of materials called metal–organic frameworks (MOFs) has been recently proposed as candidate materials demonstrating interesting new routes for multiferroism and magnetoelectric coupling. Herein, we report on the origin of multiferroicity of (CH3)2NH2Mn(HCOO)3 via direct observation of ferroelectric domains using second-harmonic generation techniques. For the first time, we observe how these domains are organized (sized in micrometer range), and how they are mutually affected by applied electric and magnetic fields. Calculations provide an estimate of the electric polarization and give insights into its microscopic origin.
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Research context
OpenAlex topics: Multiferroics and related materials · Advanced Condensed Matter Physics · Crystal Structures and Properties
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (42)
Show source-provided references
1. Fiebig, M. Revival of the magnetoelectric effect. J. Phys. D Appl. Phys 38, R123 (2005).10.1088/0022-3727/38/8/R01 ↗
2. Cheong, S. W. & Mostovoy, M. Multiferroics: a magnetic twist for ferroelectricity. Nat. Mat 6, 13–20 (2007).10.1038/nmat1804 ↗
3. Spaldin, N. A. & Fiebig, M. The renaissance of magnetoelectric multiferroics. Science 309, 391–392 (2005).10.1126/science.1113357 ↗
4. Catalan, G. & Scott, J. F. Physics and applications of bismuth ferrite. Adv. Mat 21, 2463–2485 (2009).10.1002/adma.200802849 ↗
5. Chu, Y.-H. et al. Electric-field control of local ferromagnetism using a magnetoelectric multiferroic. Nat. Mat 7, 478–482 (2008).10.1038/nmat2184 ↗
6. Gajek, M. et al. Tunnel junctions with multiferroic barriers. Nat. Mat 6, 296–302 (2007).10.1038/nmat1860 ↗
7. Hill, N. A. Why are there so few magnetic ferroelectrics? J. Phys. Chem. B 104, 6694–6709 (2000).10.1021/jp000114x ↗
8. Jain, P. et al. Synthetic magnetoelectric coupling in a nanocomposite multiferroic. Sci. Rep. 5, 9089 (2015).10.1038/srep09089 ↗
9. Catalan, G., Seidel, J., Ramesh, R. & Scott, J. F. Domain wall nanoelectronics. Rev. Mod. Phys. 84, 119–156 (2012).10.1103/RevModPhys.84.119 ↗
10. Cheetham, A. K. & Rao, C. N. R. There's room in the middle. Science 318, 58–59 (2007).10.1126/science.1147231 ↗
11. Murray, L. J., Dinca, M. & Long, J. R. Hydrogen storage in metal-organic frameworks. Chem. Soc. Rev 38, 1294–1314 (2009).10.1039/b802256a ↗
12. Jain, P. et al. Multiferroic behavior associated with an order-disorder hydrogen bonding transition in metal-organic frameworks (MOFs) with the perovskite ABX3 architecture. J. Am. Chem. Soc 131, 13625–13627 (2009).10.1021/ja904156s ↗
13. Di Sante, D., Stroppa, A., Jain, P. & Picozzi, S. Tuning the ferroelectric polarization in a multiferroic metal-organic framework. J. Am. Chem. Soc 135, 18126–18130 (2013).10.1021/ja408283a ↗
14. Jain, P., Dalal, N., Toby, B., Kroto, H. & Cheetham, A. K. Order-disorder antiferroelectric phase transition in a hybrid inorganic-organic framework with the perovskite architecture. J. Am. Chem. Soc 130, 10450–10451 (2008).10.1021/ja801952e ↗
15. Tian, Y. et al. Cross coupling between electric and magnetic orders in a multiferroic metal-organic framework. Sci. Rep 4, 6062 (2014).10.1038/srep06062 ↗
16. Tian, Y. et al. Electric control of magnetism in a multiferroic metal-organic framework. Phys. Status Solidi Rapid Res. Lett. 8, 91–94 (2014).10.1002/pssr.201308230 ↗
17. Maczka, M. et al. Temperature- and pressure-induced phase transitions in the metal formate framework of [ND4][Zn(DCOO)3] and [NH4][Zn(HCOO)3]. Inorg. Chem. 53, 9615–9624 (2014).10.1021/ic501074x ↗
18. Sanchez-Andujar, M. et al. First-order structural transition in the multiferroic perovskite-like formate [(CH3)2NH2][Mn(HCOO)3]. CrystEngComm 16, 3558–3566 (2014).10.1039/c3ce42411a ↗
19. Besara, T. et al. Mechanism of the order-disorder phase transition, and glassy behavior in the metal-organic framework [(CH3)2NH2]Zn(HCOO)3 . Proc. Natl Acad. Sci. USA 108, 6828–6832 (2011).10.1073/pnas.1102079108 ↗
20. Sanchez-Andujar, M. et al. Characterization of the order-disorder dielectric transition in the hybrid organic-inorganic perovskite-like formate Mn(HCOO)3[(CH3)2NH2]. Inorg. Chem 49, 1510–1516 (2010).10.1021/ic901872g ↗
21. Pato-Doldan, B. et al. Coexistence of magnetic and electrical order in the new perovskite-like (C3N2H5)[Mn(HCOO)3] formate. RSC Adv 3, 22404–22411 (2013).10.1039/c3ra43165g ↗
22. Wang, X. Y., Gan, L., Zhang, S. W. & Gao, S. Perovskite-like metal formates with weak ferromagnetism and as precursors to amorphous materials. Inorg. Chem. 43, 4615–4625 (2004).10.1021/ic0498081 ↗
23. Wang, W. et al. Coupling in the paramagnetic state of a metal-organic framework. Sci. Rep. 3, 2024 (2013).10.1038/srep02024 ↗
24. Abhyankar, N., Sylvain Bertaina, S. & Dalal, N. S. On Mn2+ EPR probing of the ferroelectric transition and absence of magnetoelectric coupling in dimethylammonium manganese formate (CH3)2NH2Mn(HCOO)3, a metal-organic complex with the Pb-free perovskite framework. J. Phys. Chem. C 119, 28143–28147 (2015).10.1021/acs.jpcc.5b10326 ↗
25. Fiebig, M., Pavlov, V. V. & Pisarev, R. V. Second-harmonic generation as a tool for studying electronic and magnetic structures of crystals: review. J. Opt. Soc. Am. B 22, 96–118 (2005).10.1364/JOSAB.22.000096 ↗
26. Meier, D. et al. Observation and coupling of domains in a spin-spiral multiferroic. Phys. Rev. Lett. 102, 107202 (2009).10.1103/PhysRevLett.102.107202 ↗
27. Lottermoser, T. H., Meier, D., Pisarev, R. V. & Fiebig, M. Giant coupling of second-harmonic generation to a multiferroic polarization. Phys. Rev. B 80, 100101R (2009).10.1103/PhysRevB.80.100101 ↗
28. Günter, T. et al. Spatial inhomogeneities at the LaAlO3/SrTiO3 interface: evidence from second harmonic generation. Phys. Rev. B 86, 235418 (2012).10.1103/PhysRevB.86.235418 ↗
29. Rubano, A. et al. Optical second harmonic imaging as a diagnostic tool for monitoring epitaxial oxide thin-film growth. Appl. Surf. Sci. 327, 413–417 (2015).10.1016/j.apsusc.2014.11.051 ↗
30. Lottermoser, T. & Fiebig, M. Magnetoelectric behavior of domain walls in multiferroic. Phys. Rev. B 70, 220407 (R) (2004).10.1103/PhysRevB.70.220407 ↗
31. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169 (1996).10.1103/PhysRevB.54.11169 ↗
32. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865 (1996).10.1103/PhysRevLett.77.3865 ↗
33. Heyd, J., Scuseria, G. E. & Ernzerhof, M. Hybrid functionals based on a screened Coulomb potential. J. Chem. Phys. 118, 8207–8215 (2003).10.1063/1.1564060 ↗
34. King-Smith, R. D. & Vanderbilt, D. Theory of polarization of crystalline solids. Phys. Rev. B 47, 1651 (1993).10.1103/PhysRevB.47.1651 ↗
35. Ambrosch-Draxl, C. & Sofo, J. O. Linear optical properties of solids within the full-potential linearized augmented planewave method. Comp. Phys. Commun. 175, 1–14 (2006).10.1016/j.cpc.2006.03.005 ↗
36. Hughes, J. L. P. & Sipe, J. E. Calculation of second-order optical response in semiconductors. Phys. Rev. B 53, 10751 (1996).10.1103/PhysRevB.53.10751 ↗
37. Sipe, J. E. & Ghahramani, E. d. Nonlinear optical response of semiconductors in the independent-particle approximation. Phys. Rev. B 48, 11705 (1993).10.1103/PhysRevB.48.11705 ↗
38. Sipe, J. E. & Shkrebtii, A. I. Interpretation of Raman spectra of disordered and amorphous carbon. Phys. Rev. B 61, 53337 (2000).10.1103/PhysRevB.61.5337 ↗
39. Rashkeev, S. N., Lambrecht, W. R. L. & Segall, B. Efficient ab initio method for the calculation of frequency-dependent second-order optical response in semiconductors. Phys. Rev. B 57, 3905 (1998).10.1103/PhysRevB.57.3905 ↗
40. Sharma, S., Dewhurst, J. K. & Ambrosch-Draxl, C. Linear and second-order optical response of III-V monolayer superlattices. Phys. Rev. B 67, 165332 (2003).10.1103/PhysRevB.67.165332 ↗
41. Gulans, A. et al. Exciting: a full-potential all-electron package implementing density-functional theory and many-body perturbation theory. J. Phys. Condens. Matter 26, 363202 (2014).10.1088/0953-8984/26/36/363202 ↗
42. Perdew, J.-P. & Wang, Y. Accurate and simple analytic representation of the electron-gas correlation energy. Phys. Rev. B 45, 13244 (1992).10.1103/PhysRevB.45.13244 ↗