This paper investigates strain-mediated magnetoelectricity in the multiferroic material h-ErMnO3 using Raman spectroscopy. It identifies several infrared-active phonon modes that are also Raman active and correlated with the material's order parameters and magnetic and ferroelectric properties. Temperature-dependent Raman spectroscopy was used to study how the phonon frequencies change with temperature and strain.
This paper investigates strain-mediated magnetoelectricity in the multiferroic material h-ErMnO3 using Raman spectroscopy. It identifies several infrared-active phonon modes that are also Raman active and correlated with the material's order parameters and magnetic and ferroelectric properties. Temperature-dependent Raman spectroscopy was used to study how the phonon frequencies change with temperature and strain.
This paper investigates strain-mediated magnetoelectricity in the multiferroic material h-ErMnO3 using Raman spectroscopy. It identifies several infrared-active phonon modes that are also Raman active and correlated with the material's order parameters and magnetic and ferroelectric properties. Temperature-dependent Raman spectroscopy was used to study how the phonon frequencies change with temperature and strain.
This paper investigates strain-mediated magnetoelectricity in the multiferroic material h-ErMnO3 using Raman spectroscopy. It identifies several infrared-active phonon modes that are also Raman active and correlated with the material's order parameters and magnetic and ferroelectric properties. Temperature-dependent Raman spectroscopy was used to study how the phonon frequencies change with temperature and strain.
Strain-mediated magnetoelectricity probed by Raman spectroscopy in h-ErMnO3
A. Correa ,1 D. A. B. Barbosa ,2 A. S. de Menezes ,1 C. L. Valente-Rodrigues ,3
Surender Kumar Sharma ,4,1 and C. C. Santos 1,* 1 Departamento de Física, Universidade Federal do Maranhão, 65080-805 São Luís, Maranhão, Brazil 2 Coordenação de Licenciatura em Ciências Naturais - Física, Universidade Federal do Maranhão, 65418-000 Bacabal, Maranhão, Brazil 3 Centro Brasileiro de Pesquisas Físicas, 22290-180 Rio de Janeiro, Rio de Janeiro, Brazil 4 Department of Physics, Central University of Punjab, 151 401 Bathinda, India
(Received 12 December 2022; revised 24 May 2023; accepted 8 June 2023; published 5 July 2023)
We show the role of strain in magnetoelectric effect through coupling between order parameters and their interplay using infrared/Raman-active optical phonons in hexagonal manganite (h-ErMnO3 ). The magnetoelec- tric coupling is arbitrated through strain from infrared-active phonons, which by symmetry are also Raman active. The identification of the primitive order parameters by spin-phonon coupling opens a promising avenue to realize the strategy based on coupling of spins, optical phonons, and strain to create magnetoelectrics with strain-mediated interaction through spin-lattice coupling in bulk inducing a ferromagnetic-ferroelectric state in an antiferromagnetic-paraelectric phase.
DOI: 10.1103/PhysRevB.108.014101
Multiferroics materials present at least two ferroic orders roelectric order in h-ErMnO3 is related to dislocation of the Er namely ferroelectricity, ferromagnetism, ferroelasticity, anti- ion in the c axis, and the antiferromagnetic order is connected ferromagnetism, and ferrotoroidicity in the same phase [1]. to both angles. Further, very recent density functional theory Magnetoelectrics are multiferroics in which ferroelectricity (DFT) calculations suggested that manganese and oxygen dis- and ferromagnetism are coupled directly or indirectly via placements at the ab plane of the MnO5 breathing mode in strain and the change in electrical properties occur by mag- ErMnO3 can be used to control magnetic order [8]. netic fields or vice versa. The coupling coefficient of directly As mentioned before, only IR-active phonons contribute coupled magnetoelectrics is linear with electric or magnetic to magnetoelectricity. However, for h-ErMnO3 , all infrared fields. For indirect coupling, cross terms are proportional to phonons are also Raman active. Therefore, we applied Raman strain with quadratic dependence on electric and magnetic spectroscopy to investigate the atomic displacements related fields [2]. Such possibility motivated the elaboration of a to order parameters responsible for magnetoelectric coupling strategy to create magnetoelectrics with strain-mediated in- at low temperatures in h-ErMnO3 . A detailed synthesis and teraction of ferroelectricity and antiferromagnetism using a characterization procedure is given in Ref. [9]. The influence strong coupling of strain and infrared (IR) active phonons in of negative expansion of the c axis and the magnetostriction an antiferromagnetic-paraelectric bulk phase especially pro- is also investigated. The displacements of the ions related posed to thin films engineering [3] since ferroelectric and to the order parameters are connected with the 118-, 298-, antiferromagnetic domains are coincident in these materials and 686-cm−1 modes in Raman spectra. These phonon [4]. The realization of this proposition showed that spin- wavenumbers showed an intricate dependence on tempera- phonon coupling opens a promising avenue to investigate the ture due to several concurrent mechanisms. The 232-cm−1 coupled order parameters via their wavenumber dependencies mode showed a clear quadratic wavenumber dependence on temperature [5]. with temperature over the entire range of a primary order Recently, Giraldo et al. [6] showed that h-ErMnO3 has parameter. strong magnetoelectric coupling in bulk despite the absence In this paper, we used temperature-dependent Raman spec- of a linear magnetoelectric effect. Also, Skjærvo et al. [7] troscopy to investigate local structural features in h-ErMnO3 . reported a meticulous neutron diffraction investigation of the The ErMnO3 hexagonal structure with space group P63 cm atomic structure from room temperature to 1273 K, describing has 23 IR-active modes that are also Raman active due local structure and order parameters for YMnO3 , which is an to its noncentrosymmetric symmetry. Thus, h-ErMnO3 has isostructural manganite. According to this work, the atomic a total of 38 Raman-active modes distributed as Raman = displacements related to the order parameter that governs 9A1 ⊕ 15E2 ⊕ 14E1 being the IR-active modes represented the magnetoelectric coupling in hexagonal perovskites are by IR = 9A1 ⊕ 14E1 . The Raman spectrum at 300 K for (i) bipyramidal tilting in the c axis (O1-Mn-O2 angle), (ii) h-ErMnO3 is typical for hexagonal perovskites [10,11] and bipyramidal tilting in the ab plane (O3-Mn-O4 angle), and (iii) shows, in general, 14 bands (see Fig. S4 and Table S2 of off-centering displacement of the rare-earth ion [7]. Then, fer- the Supplemental Material [9]). We selected and analyzed six bands in more detail, whose classification and atomic movements are described in Table I. A comparison between * Corresponding author: [email protected] these six selected phonons in h-ErMnO3 and a single crystal
