# Fileset
[ESI-Ca05Mn15MnWO6-160724.pdf](https://mdr.nims.go.jp/filesets/7bcbf0d7-17d6-4f93-bcce-0ff2a0c7c117/download)
## Creator
[Alexei A. Belik](https://orcid.org/0000-0001-9031-2355)
## Rights
This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry Letters, copyright © 2024 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.chemmater.4c01720[In Copyright](http://rightsstatements.org/vocab/InC/1.0/)
## Other metadata
[Hybrid Multiferroic Behavior in the Double Perovskite (Ca0.5Mn1.5)MnWO6](https://mdr.nims.go.jp/datasets/bb66e54f-b27d-4a92-847a-6119e9d51a02)
## Fulltext
Supporting Information (Online Material) for Supporting Information (Online Material) for Hybrid Multiferroic Behavior in the Double Perovskite (Ca0.5Mn1.5)MnWO6 Alexei A. Belik* Research Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), Namiki 1-1, Tsukuba, Ibaraki 305-0044, Japan E-mail: Alexei.Belik@nims.go.jp S1mailto:Alexei.Belik@nims.go.jp -0.00100.0010.0020.0030 20 40 60 80 100 120301 Hz 903 Hz2.71 kHz 8.16 kHz24.5 kHz 73.7 kHz-0.002-0.00100.0010.0020.0030 20 40 60 80 100 120301 Hz 903 Hz2.71 kHz 8.16 kHz24.5 kHz 73.7 kHz(Ca0.3Mn1.7)MnWO6 (Ca0.5Mn1.5)MnWO6 Temperature (K) Temperature (K) Dielectric Loss Dielectric Loss (a) (b) Figure S1. Temperature dependence of dielectric loss in (a) (Ca0.5Mn1.5)MnWO6 and (b) (Ca0.3Mn1.7)MnWO6 between T = 3 K and 120 K at different frequencies (f from 301 Hz to 73.7 kHz) at zero magnetic field. S2 (Ca0.5Mn1.5)MnWO6 @ 73.7 kHz, T = 27−180 K Instrumental artifact from ice Maxwell-Wagner contribution Temperature (K) Dielectric constant 697173757779810 50 100 150 200 250 300301 Hz903 Hz2.71 kHz8.16 kHz24.5 kHz73.7 kHzfitFigure S2. Temperature dependence of dielectric constant of (Ca0.5Mn1.5)MnWO6 between T = 3 K and 300 K at different frequencies (f from 301 Hz to 73.7 kHz) at zero magnetic field. The black line shows a fit (between 27 K and 180 K using data at f = 73.7 kHz) by the Curie-Weiss law, where the calculated curve was extended down to 3 K and up to 300 K using the obtained fitted parameters. Anomalies near 250 K (highlighted by a broken oval) are instrumental artifacts originating from ice as such anomalies were observed in many other samples measured on the same instrument (PPMS). Maxwell-Wagner contributions at low frequencies are highlighted by a broken oval. S3 7075808590950 50 100 150 200 250 300301 Hz903 Hz2.71 kHz8.16 kHz24.5 kHz73.7 kHz7075808590951001050 50 100 150 200 250 30073.7 kHz, 0 Oe, cooling73.7 kHz, 0 Oe, heating73.7 kHz, 0 Oe, cooling73.7 kHz, 0 Oe, heatingfit(Ca0.3Mn1.7)MnWO6 @ 73.7 kHz, T = 40−180 K Eq.: ε(T) = ε0 + C/(T−θ) ε0 = 60.35(4) C = 5675(17) Kθ = −119.2(3) KTC = TN = 27 K Dielectric constant Temperature (K) Instrumental artifact from ice(Ca0.3Mn1.7)MnWO6 Instrumental artifact from ice Maxwell-Wagner contribution Temperature (K) Dielectric constant cooling at H = 0 Oe H = 0 Oe (a)(b) Figure S3. (a) Temperature dependence of dielectric constant of (Ca0.3Mn1.7)MnWO6 between T = 3 K and 300 K at one frequency of 73.7 kHz at zero magnetic field on cooling and heating (two runs). The black line shows a fit (between 40 K and 180 K) by the Curie-Weiss law, where the calculated curve was extended down to 3 K and up to 300 K using the obtained fitted parameters. Anomalies near 250 K (highlighted by a broken oval) are instrumental artifacts originating from ice. (b) Temperature dependence of dielectric constant of (Ca0.3Mn1.7)MnWO6 between T = 3 K and 300 K at different frequencies (f from 301 Hz to 73.7 kHz) at zero magnetic field. Maxwell-Wagner contributions at low frequencies are highlighted by a broken oval. S4 -0.8-0.40.00.40.8-80 -40 0 40 80Magnetic Field (kOe)Magnetization ( µB / f.u.) T = 5 K(Ca0.5Mn1.5)MnWO6 (Ca0.3Mn1.7)MnWO6 (b) (a) Magnetic Field (kOe)Magnetization (µB / f.u.) T = 5 K-0.8-0.40.00.40.8-80 -40 0 40 80 Figure S4. (a) An M versus H curve of (Ca0.5Mn1.5)MnWO6 at T = 5 K. (b) An M versus H curve of (Ca0.3Mn1.7)MnWO6 at T = 5 K. S5 01020304050600 50 100 150 200 250 30059.759.960.160.360.560.760.90 50 100 150 200301 Hz903 Hz2.71 kHz8.16 kHz24.5 kHz73.7 kHzDielectric constant Temperature (K) Temperature (K) Dielectric loss TN = 16 K Maxwell-Wagner contribution Instrumental artifact from ice Ca2MnWO6 H = 0 Oe (a) (b) -0.0050.0000.0050.0100 50 100 150 200301 Hz 903 Hz2.71 kHz 8.16 kHz24.5 kHz 73.7 kHzFigure S5. (a) Temperature dependence of dielectric constant of Ca2MnWO6 between T = 3 K and 300 K at different frequencies at zero magnetic field. Anomalies near 250 K (highlighted by a broken oval) are instrumental artifacts originating from ice. Maxwell-Wagner contributions at low frequencies are highlighted by a broken oval. Inset shows details between 3 K and 230 K. (b) Temperature dependence of dielectric loss of Ca2MnWO6 below 220 K. S6 0.00.30.60.91.20 10 20 30 40 50036912 Ca2CaWO6 Ca2MnWO6 Cmag SmagC / T (J K−2 mol−1) Temperature (K) Sm (J K−1 mol −1) Cp/T: Ca2MnWO6Cp/T: Ca2CaWO6, lattice Cm/T: Ca2MnWO6Sm: Ca2MnWO6 Cp/T: Ca2MnWO6, 90 kOe Figure S6. Specific heat data for Ca2MnWO6. White circles: Cp/T versus T at H = 0 Oe; black circles: Cm/T versus T at H = 0 Oe (where Cm is the magnetic part of specific heat); blue triangles and the right-hand axis: Sm versus T at H = 0 Oe (where Sm is magnetic entropy); red small circles: Cp/T versus T at H = 90 kOe. Gray circles show Cp/T versus T data at H = 0 Oe for Ca2CaWO6, which can serve as a lattice estimation. All data were measured on cooling. The experimental magnetic entropy of 13.57 J K−1 mol−1 was close to the expected value of 14.90 J K−1 mol−1 for Mn2+. S7 -0.6-0.4-0.20.00.20.40.6-80 -60 -40 -20 0 20 40 60 80y = 0.2309x + 14.191R2 = 0.99970.000.010.020.030.040.050 50 100 150 200 250 300020406080χ (emu×mol− 1× Oe−1 ) Temperature (K) χ−1 (emu−1×mol×Oe) µeff = 5.886(12)µB θ = −61.5(1.3) K µcalc = 5.916µB T N = 16 K Magnetic Field (kOe) Magnetization (µB / f.u.) T = 5 KCa2MnWO6 Ca2MnWO6 (b) (a) Figure S7. (a) A field-cooled on cooling (FCC) dc magnetic susceptibility (χ = M/H) curve of Ca2MnWO6 measured at H = 10 kOe. Right-hand axis shows the χ−1 versus T curve with the Curie-Weiss fit (black line). Parameters of the fit are shown on the figure. (b) An M versus H curve of Ca2MnWO6 at T = 5 K. S8 0.00.30.60.91.20 20 40 60 80 10001020300 Oe, cooling90 kOe, coolinglatticeCm/TSmC / T (J K−2 mol−1) Sm (J K−1 mol −1) Temperature (K) (CaMn)MnWO6 P21/n Cm/T Sm Figure S8. Specific heat data for (CaMn)MnWO6 (P21/n modification). White circles: Cp/T versus T at H = 0 Oe; black circles: Cm/T versus T at H = 0 Oe (where Cm is the magnetic part of specific heat); blue triangles and the right-hand axis: Sm versus T at H = 0 Oe (where Sm is magnetic entropy); red small circles: Cp/T versus T at H = 90 kOe. Gray circles show a lattice contribution (Clat/T versus T) at H = 0 Oe, where Clat is Cp for Ca2CaWO6 between 2 K and 46 K and Cp for Ca2MnWO6 between 48 K and 100 K. All data were measured on cooling. The experimental magnetic entropy of about 30.9 J K−1 mol−1 was close to the expected value of 29.8 J K−1 mol−1 for 2Mn2+. A broad anomaly is only seen due to short-range magnetic ordering. A very weak anomaly near 45 K is from a ferrimagnetic long-range ordering in the P42/n modification. S9 -0.00200.0020.0040.0060 50 100 150301 Hz 903 Hz2.71 kHz 8.16 kHz24.5 kHz 73.7 kHz1201251301350 50 100 150Temperature (K) Dielectric constant Dielectric Loss (a)(b)(CaMn)MnWO6 P21/n (CaMn)MnWO6 P21/n Figure S9. (a) Temperature dependence of dielectric constant of (CaMn)MnWO6 (P21/n modification) between T = 3 K and 180 K at different frequencies at zero magnetic field. (b) Temperature dependence of dielectric loss of (CaMn)MnWO6. Relaxation-like behavior clearly seen near 50 K in the shifts of dielectric loss peaks as a function of frequency can be explained by a small admixture of the P42/n modification and interfacial effects. Note that the P42/n modification has a long-range ferrimagnetic transition at 45 K. S10