Large Linear Magnetoelectric Effect and Field-Induced Ferromagnetism
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Shen et al. NPG Asia Materials (2019) 11:50 https://doi.org/10.1038/s41427-019-0151-9 NPG Asia Materials ARTICLE Open Access Large linear magnetoelectric effect and field-induced ferromagnetism and ferroelectricity in DyCrO4 Xudong Shen1,2, Long Zhou1,2, Yisheng Chai1,3,YanWu4, Zhehong Liu1,2,YunyuYin1,2,HuiboCao4, Clarina Dela Cruz4, Young Sun 1,2, Changqing Jin1,2,AngelMuñoz5,JoséAntonio Alonso 6 and Youwen Long1,2,7 Abstract All the magnetoelectric properties of scheelite-type DyCrO4 are characterized by temperature- and field- dependent magnetization, specific heat, permittivity, electric polarization, and neutron diffraction measurements. Upon application of a magnetic field within ±3 T, the nonpolar collinear antiferromagnetic structure leads to a large linear magnetoelectric effect with a considerable coupling coefficient. An applied electric field can induce the converse linear magnetoelectric effect, realizing magnetic field control of ferroelectricity and electric field control of magnetism. Furthermore, a higher magnetic field (>3 T) can cause a metamagnetic transition from the initially collinear antiferromagnetic structure to a canted structure, generating a large ferromagnetic magnetization −1 up to 7.0 μB f.u. Moreover, the new spin structure can break the space inversion symmetry, yielding ferroelectric polarization, which leads to coupling of ferromagnetism and ferroelectricity with a large ferromagnetic component. 1234567890():,; 1234567890():,; 1234567890():,; 1234567890():,; Introduction maximum α obtained for a nonpolar antiferromagnetic − The linear magnetoelectric (ME) effect and multi- (AFM) structure is <40 ps m 1 usually6. It is important to ferroicity enable control of polarization P (magnetization obtain a larger and constant ME effect in wider tem- M) by a magnetic (electric) field, which is beneficial for perature and/or magnetic field regions for potential applications in spintronic devices, nonvolatile memories, applications. – high-sensitivity magnetic field sensors, etc1 5. In the linear In the 1990s, the term “multiferroics” was proposed to ME effect, the induced electric polarization or magneti- describe materials that simultaneously exhibit more than zation is proportional to the applied magnetic field H or one ferroic order, such as ferromagnetism, ferroelectricity, 10 electric field E, which can be expressed as P = αH or μ0M and ferroelasticity, in a single phase . Among the dif- 6,7 = αE , where α denotes the linear ME coefficient and μ0 ferent multiferroics, the spin-ordering-induced ferro- denotes the magnetic permeability of a vacuum. Since the electrics (i.e., ME multiferroics) attracted significant 11–15 first observation of the linear ME effect in Cr2O3 in the attention owing to the strong ME coupling . Based on 1960s8,9, the search for single-phase ME materials with the magnetic space group, collinear ferromagnetic (FM) larger α values has attracted much attention. The spin alignment cannot break the spatial inversion sym- metry. Therefore, electric polarization in single-phase ME multiferroics is often induced by some peculiar AFM or Correspondence: Youwen Long ([email protected]) canted AFM spin structures instead of collinear ferro- 1Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, magnetism16. Consequently, the magnetic moment is too – Chinese Academy of Sciences, Beijing 100190, China small to be effectively controlled17 19. It is very challen- 2School of Physics, University of Chinese Academy of Sciences, Beijing 100049, China ging to obtain a material with strongly coupled Full list of author information is available at the end of the article. © The Author(s) 2019 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 linktotheCreativeCommons 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/. Shen et al. NPG Asia Materials (2019) 11:50 Page 2 of 8 FM–ferroelectric properties and a considerable magnetic system (Quantum Design, MPMS-3). Both zero field- moment. cooling (FC) and FC modes were employed for χ mea- 5+ DyCrO4 has a rare Cr valence state. Under ambient surements at 0.01 T. The field-dependent M measure- conditions, it crystallizes into a zircon-type crystal struc- ments were performed at different temperatures. The 20,21 ture with the space group of I41/amd . An FM phase specific heat (Cp) and electrical properties were measured transition with a large magnetocaloric effect occurs at using a physical property measurement system (Quantum 22–24 approximately 23 K . Moreover, the zircon-type Design, PPMS-9T). The Cp data were acquired during structure is sensitive to external pressure. A pressure- cooling in the range of 50–2 K with different magnetic induced irreversible structural phase transition toward a fields. For the measurements of the relative dielectric scheelite-type new phase with I41/a symmetry has already constant εr, dielectric loss tanδ, and pyroelectric current been reported25. In contrast to the FM zircon phase, the density (J), the specimens were fabricated as thin plates – scheelite phase exhibits a long-range AFM transition26 28. with a typical surface area of 1–2mm2 and a thickness of In this study, scheelite-type DyCrO4 was prepared in a 0.2 mm. Silver electrodes were coated onto the two sur- polycrystalline form by a high-pressure and moderate- faces of the plate for electrical measurements. Different temperature treatment method (see “Materials and frequencies of 1 kHz, 10 kHz, 0.1 MHz, and 1 MHz were methods” below). Based on the powder X-ray diffraction applied for the dielectric constant and dielectric loss (XRD) and neutron diffraction results, there is no dis- measurements at selected magnetic fields in the range of cernable impurity phase, such as the residual FM zircon 0–9 T with intervals of 1 T using an Agilent E4980A phase, or decomposed DyCrO3 perovskite phase (see Precision LCR Meter while sweeping the temperature − Supplementary Figs. S1 and S2 for details). This com- from 2 to 50 K with a heating rate of 2 K min 1. The pound has a nonpolar collinear AFM ground state with pyroelectric current was measured by a Keithley 6517B zero magnetic field. Within μ0H ≈ ±3 T, a large and almost precise electrometer while sweeping the temperature − constant linear ME effect is observed, enabling H control from 2 to 50 K at a rate of 2 K min 1. Before this mea- of P and E control of M. Under higher magnetic fields, a surement, the sample was poled from 50 to 2 K with a −1 metamagnetic transition occurs and is accompanied by a poling electric field of Epol = ±1.08 MV m . Once the large FM magnetization. Furthermore, the new spin temperature was decreased to 2 K, Epol was switched off structure can break the spatial inversion symmetry and and J was measured as described above. The magnetic- thereby generate ferroelectric polarization. The presented field-dependent current was measured while sweeping the −1 DyCrO4 paves the way for novel investigations on magnetic field at a rate of 0.01 T s . In these measure- simultaneous direct and converse linear ME effects and ments, the PPMS was used to provide low-temperature FM–ferroelectrics with large magnetic moments. and magnetic field environments. The electric polariza- tion (P) was obtained by integrating J as a function of Materials and methods time. In addition, we measured the electric-field-induced Sample synthesis and XRD magnetization using MPMS-3 with different electric fields To fabricate the scheelite-type DyCrO4 sample, the produced by the Keithley 6517B electrometer. Before the zircon-type sample was prepared at ambient pressure as a measurement, the sample was cooled from 50 to 10 K at a 26 −1 −1 precursor, as reported in a previous study . The prepared rate of 2 K min at Epol = 0.5 MV m and μ0H = 4T. zircon-type DyCrO4 powders were pressed into a golden Once the temperature was decreased to 10 K, both Epol cylinder with a diameter of 4.0 mm and height of 3.0 mm. and H were switched off, and then M was measured The cylinder was treated at 6–8 GPa and 700–750 K for during heating from 10 to 26.5 K at fixed temperatures 10–30 min on a cubic-anvil-type high-pressure apparatus and selected electric fields. using pyrophyllite as a pressure transmission medium. When the heating power was turned off, the pressure was Neutron diffraction measurements slowly released. The crystal quality and structure were The neutron powder diffraction (NPD) measurements analyzed by powder XRD using a Huber diffractometer were carried out using the constant-wavelength high- with Cu Kα1 radiation at 40 kV and 30 mA. The XRD data resolution neutron powder diffractometer HB2A at Oak were acquired at room temperature in the 2θ range of Ridge National Laboratory (ORNL). The temperature was 10°–100° with steps of 0.005° and analyzed by Rietveld controlled by a Lakeshore Bridge, while the magnetic field refinement using the GSAS software29. was generated by an Oxford-5 T superconducting magnet. The temperature-dependent diffraction profiles were Magnetic, specific heat, dielectric, and pyroelectric current measured at a wavelength of λ = 2.41 Å with the colli- measurements mation out-high intensity mode. The overall powder mass The magnetic susceptibility (χ) and magnetization (M) was 1.3 g.