# Fileset

[InorgChem-V62-20042-Dy2CuZnMn4O12-ESI.pdf](https://mdr.nims.go.jp/filesets/354c1126-da0c-4b0e-879f-9e73224a0ae1/download)

## Creator

[Alexei A. Belik](https://orcid.org/0000-0001-9031-2355)

## Rights

[Creative Commons BY-NC-ND Attribution-NonCommercial-NoDerivs 4.0 International](https://creativecommons.org/licenses/by-nc-nd/4.0/)

## Other metadata

[Anisotropic Thermal Expansion and a Second-Order Charge Order Transition in the Ferrimagnetic Dy<sub>2</sub>CuZnMn<sub>4</sub>O<sub>12</sub> Perovskite with Triple A-Site Cation Ordering](https://mdr.nims.go.jp/datasets/1026b300-04e9-48b3-b044-036419cdc26d)

## Fulltext

Supporting Information (Online Material) for Supporting Information (Online Material) for      Anisotropic Thermal Expansion and a Second-order Charge Order Transition in the Ferrimagnetic Dy2CuZnMn4O12 Perovskite with Triple A-site Cation Ordering   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.jpTable S1. Selected Bond Lengths (l (Å) < 2.8 Å), Bond Angles (deg), Bond Valence Sums, BVS, and Distortion Parameters of MnO6, ∆, in Dy2CuZnMn4O12 at 100 K a Dy1–O5 ×2 Dy1–O3 ×2 Dy1–O2 ×2 Dy1–O1 ×4 BVS(Dy13+)  2.289(9) 2.340(8) 2.400(9) 2.656(7) +3.39 Dy2–O2 ×2 Dy2–O4 ×2 Dy2–O5 ×2 Dy2–O1 ×4 BVS(Dy23+) 2.336(9) 2.378(9) 2.418(9) 2.641(7) +3.18 Cu–O1 ×4 BVS(Cu2+)  1.951(3) +1.92  Zn–O3 ×2 Zn–O4 ×2 BVS(Zn2+)  1.965(9) 2.044(9) +1.79  Mn1–O2 ×2 Mn1–O3 ×2 Mn1–O1 ×2 BVS(Mn13+) ∆(Mn1–O)  1.890(2) 1.963(3) 2.129(7) +3.30 25.0×10−4 Mn2–O5 ×2 Mn2–O4 ×2 Mn2–O1 ×2 BVS(Mn24+) BVS(Mn23+) ∆(Mn2–O)  1.901(2) 1.932(3) 1.946(8) +3.76 +3.84 1.0×10−4 Mn1–O1–Mn2 ×2 Mn1–O2–Mn1 Mn1–O3–Mn1 144.84(9) 147.53(9) 134.91(9) Mn2–O4–Mn2 Mn2–O5–Mn2 139.94(9) 145.03(9)  a BVS = ∑ , ν=Nii1ν i = exp[(R0 − li)/B], N is the coordination number, B = 0.37, R0(Dy3+) = 2.036, R0(Cu2+) = 1.679, R0(Zn2+) = 1.704, R0(Mn4+) = 1.753, and R0(Mn3+) = 1.76.  S2  Figure S1. Photographs of the as-synthesized Dy2CuZnMn4O12 sample. This figure shows that the as-synthesized sample was a highly fragile pellet, which fell into powder when touched.  S3  -0.5-0.4-0.3-0.2-0.10.0120 220 320 420 520 6201st heating1st cooling2nd heating2nd cooling-0.10-0.050.000.050.100.15300 400 500 600 7001st heating1st cooling2nd heating2nd coolingHeat flow (W/g) (a) heating Heat flow (W/g) (b) cooling Temperature (K) TCO TCO Dy2CuZnMn4O12, 14.20 mg  Figure S2. Differential scanning calorimetry (DSC) curves of a powder sample of Dy2CuZnMn4O12 (14.20 mg) on (a) heating and (b) cooling. The arrows show the charge-order phase transition temperature determined by high-temperature synchrotron X-ray powder diffraction – no anomalies were detected at this temperature by DSC.   S4   01020304050607080901000 50 100 150ZFC, 100 OeFCC, 100 Oe0204060801000 20 40 60 80 100 120 140ZFC, 100 OeFCC, 100 Oeχ  (emu×mol−1× Oe−1 ) dχT/dT (emu×mol−1× Oe−1 ) Temperature (K) Temperature (K) 45 K 35 K Dy2CuZnMn4O12 Dy2CuZnMn4O12 (a)(b)  Figure S3. (a) A fragment of the ZFC and FCC dχT/dT versus T curves of Dy2CuZnMn4O12 at H = 100 Oe to emphasize anomalies near 35–45 K. (b) The ZFC and FCC χ versus T curves of Dy2CuZnMn4O12 at H = 100 Oe below 155 K.  S5  024681012140 50 100 150 200 250 300 350 400 450 500H = 70 kOeχ−1  (emu−1 ×mol× Oe) Temperature (K)  Figure S4. (Raw/uncorrected) high-temperature inverse χ−1 versus T curve of Dy2CuZnMn4O12 at H = 70 kOe measured from 300 K to 470 K. A small deviation from the linear behavior at high temperatures is caused by a temperature-independent contribution from a sample holder. There were no detectable anomalies near TCO = 425 K.   S6  -24-18-12-606121824-8 -6 -4 -2 0 2 4 6 8Magnetization  (µB / f.u.) Magnetic Field (kOe) Dy2CuZnMn4O12 5 K 25 K60 K100 K-30-20-100102030-80 -60 -40 -20 0 20 40 60 80Magnetization  (µB / f.u.) Magnetic Field (kOe) Dy2CuZnMn4O12, 25 K Dy2CuMnMn4O12, 5 K MS = 24.3µB MS = 19.8µB (a)(b) Figure S5. (a) A zoomed part of the M versus H curves of Dy2CuZnMn4O12 at T = 5 K, 25 K, 60 K, and 100 K. (b) Comparison of the M versus H curves of Dy2CuZnMn4O12 at T = 25 K (blue triangles) and Dy2CuMnMn4O12 at T = 5 K (black circles) – the curves were qualitatively similar.  S7  -0.20.00.20.40.60.80 20 40 60 80 100 120 1400.5 Hz2 Hz7 Hz25 Hz110 Hz500 Hz-0.50.00.51.01.52.02.50 20 40 60 80 100 120 1400.1 Oe0.5 Oe5 Oe051015200 20 40 60 80 100 120 1400.1 Oe0.5 Oe5 Oe051015200 20 40 60 80 100 120 1400.5 Hz2 Hz7 Hz25 Hz110 Hz500 Hzχ  ′  (emu×mol−1× Oe−1 ) χ  ′′  (emu×mol−1× Oe−1 ) Temperature (K) Hac = 0.5 Oe Hdc = 0 Oe Hac = 0.5 Oe Hdc = 0 Oe (a) (b) (c) (d) f = 300 Hz Hdc = 0 Oe f = 300 Hz Hdc = 0 Oe Hac =  Hac =  f =  f =  Dy2CuZnMn4O12 -0.10.10.30 40 80 120-0.050.050.150 20 40 60 80 Figure S6. (a) The χ′ versus T and (b) χ′′ versus T curves of Dy2CuZnMn4O12 at different frequencies measured with Hac = 0.5 Oe and Hdc = 0 Oe. (c) The χ′ versus T and (d) χ′′ versus T curves at different Hac = 0.1, 0.5, and 5 Oe and one frequency of 300 Hz (Hdc = 0 Oe). Insets show zoomed parts of the corresponding figures. The dotted oval on panel (b) emphasizes (most probably) measurement artifacts because the measurement steps changed exactly at this temperature range.  S8 BVS(Cu2+) BVS(Zn2+) BVS(Mn13+) BVS(Mn24+)