Journal of Sol-Gel Science and Technology (2021) 97:663–671

https://doi.org/10.1007/s10971-021-05476-3

ORIGINAL PAPER: SOL-GEL AND HYBRID MATERIALS FOR DIELECTRIC,

ELECTRONIC, MAGNETIC AND FERROELECTRIC APPLICATIONS

Influence of Al3+ doping on the magnetism of one-dimensional

frustrated Ca3CoMnO6 compound
Yongqiang Wang1 Jin Zhou1 Chenfei Shi1 Gaoshang Gong
● ● ●
1 ●
Huiyun Hu1 Yuling Su1
●

Received: 28 September 2020 / Accepted: 13 January 2021 / Published online: 8 February 2021
© The Author(s), under exclusive licence to Springer Science+Business Media, LLC part of Springer Nature 2021

Abstract
Previous reports depict that the nonstoichiometric Co/Mn ratio greatly affects the physical properties of Ca3CoMnO6, but
few papers focus on the Co/Mn site doping effect. In order to investigate the influence of the substitution on the
magnetization, partial Mn4+ ions were replaced with Al3+ ions and polycrystalline Ca3CoMn1-xAlxO6 (x = 0, 0.05, 0.1, 0.15,
0.2) samples were prepared. All the samples crystallized into rhombohedral structure without existence of impurities. SEM
patterns showed that the mean particle size decreased with the introduction of Al element. Due to the dilution effect of
1234567890();,:
1234567890();,:

nonmagnetic Al3+ ions to the spin chains, the competing short-range antiferromagnetic/ferromagnetic order caused by the
“order by disorder” phenomenon was suppressed. The high-temperature spin freezing peak disappeared gradually and the
doped samples presented a faster dynamic behavior, indicating a more robust long-range antiferromagnetic order. The time-
dependent magnetization showed a nonmonotonic relaxation in a field of 5T, implying the possible existence of quantum
tunneling of magnetization.

Graphical Abstract
Ca3CoMn1-xAlxO6 (x = 0, 0.05, 0.1, 0.15, 0.2) samples were synthesized and all of them crystallized into single-phase
rhombohedral structure. Due to the dilution effect of the nonmagnetic Al3+ ions to the …Co2+-Mn4+-Co2+-Mn4+…spin
chains, the high-temperature spin freezing peak disappears gradually and a faster dynamic behavior in the doped samples is
observed. Our investigation confirms that the substitution of the nonmagnetic Al3+ ions has a similar effect with the Co/Mn
defection. This is to say that the nonmagnetic doping could also suppress the formation of short-range magnetic correlation
and help in building a more robust long-range antiferromagnetic order. For the nonmonotonic relaxation of the time-
dependent magnetization, it implies the possible existence of quantum tunneling of magnetization. The normalized time-
dependent M/M0 curves for Ca3CoMn1-xAlxO6(x = 0, 0.05, 0.1, 0.15, 0.2) measured at 5 K. (1) The magnetization was
measured by cooling the samples down to 5K, a field of 5T was applied and kept for 10 min, switching off the field and the
remanent magnetization was recorded. (2) The magnetization was measured by cooling the samples down to 5 K firstly and
the magnetic field was switched on, as well as field reaches 5T the magnetization was recorded immediately.

* Gaoshang Gong
gonggaoshang@zzuli.edu.cn
1
School of Physics and Electronic Engineering, Zhengzhou
University of Light Industry, Zhengzhou 450002, PR China
664 Journal of Sol-Gel Science and Technology (2021) 97:663–671

Keywords Spin chain Frustration Magnetic order Phase transition

● ● ●

Highlights
● Doping with nonmagnetic Al3+ weaks the formation of short range magnetic order and help to establish a more robust
long rang antiferromagnetic order in Ca3CoMnO6.
● The dilution effect causes the high-temperature spin freezing peak disappears gradually and a faster dynamic behavior is
observed.
● Nonmonotonic relaxation implies the possible existence of quantum tunneling of magnetization.

1 Introduction octahedral site [18]. Along c axis, there is an alternating

Materials that contain (anti)ferromagnetic and (anti)fer-
roelectric orders are named as multiferroic materials
[1–6]. The switch of improper ferroelectricity associated
with magnetic field and vice versa holds great potential
applications [7]. For conventional ferroelectricity, tran-
sition metal ions with d0 electronic configuration are
needed for promoting the ferroelectric distortion while
for ferromagnetism the transition metal ions should have
partially filled d orbital [8–10]. This conflict causes the
multiferroic materials to only exist in that systems that
contain both ferroelectric active ions and magnetic ions in
different crystallographic sites (type-I multiferroics)
[11, 12], Alternately, they can exist in the systems in
which space inversion symmetry can be broken by
magnetic order (type-II multiferroics) [13, 14]. Unlike the
independent origins of ferroelectric order and magnetic
order in type-I multiferroics, the polarization in type-II
multiferroics stems directly from the magnetic exchange
interaction. This has resulted to a large magnetoelectric
coupling coefficient and rich physical mechanism, which
have attracted considerable attention in the past years
[15–17].
As one kind of type-II multiferroics, the frustrated
Ca3CoMnO6 compound crystalizes into the K4CdCl6 derived
structure, where the smaller Mn4+ ions prefer to occupy the
arrangement of MnoctO6 octahedra and CotrigO6 trigonal
prisms, which establishes the …Co2+-Mn4+-Co2+-Mn4+…
ionic/charge order and forms ↑↑↓↓ spin structure [19]. Dif-
ferent from the inverse Dzyaloshinskii–Moriya model where
a local electric polarization is induced via spin–orbit inter-
action of two noncollinear magnetic moments and the Arima
model where a local polarization is induced by the spin-
dependent p-d hybridization [20, 21], the electric polariza-
tion of Ca3CoMnO6 originates from the symmetric spin
exchange interaction of magnetically inequivalent ions (S =
3/2 for Mn4+ spins and S = 1/2 for Co2+) [22]. According to
previous reports, the magnetic structural change influences
the ferroelectricity greatly. The perfect Co/Mn ionic order
causes the loss of the ↑↑↓↓ long-range order and the emer-
gence of short-range magnetic correlation, leading to a
suppressed polarization [19, 23]. On the other hand, in Co/
Mn defective Ca3Co1-xMnO6/ Ca3CoMn1-xO6, the short-
range magnetic correlation disappears and an enhanced
ferroelectric polarization can be obtained [24]. Therefore,
tuning the magnetic structure of Ca3CoMnO6 seems very
meaningful. Nevertheless, the related literature shows few
papers focus on the Co/Mn site doping effect.
As the Al3+ ions can enter into the lattice of the iso-
structural Ca3Co2O6 [25], it is believed that Al3+ ions could
also be introduced into Ca3CoMnO6. The dilution effect of
the nonmagnetic substitution to the correlation interaction
Journal of Sol-Gel Science and Technology (2021) 97:663–671
may release the magnetic frustration and optimize the
magnetic structure of Ca3CoMnO6. In this work, the Al3+
doped Ca3CoMn1-xAlxO6 compounds were synthesized. The
magnetization measurements indicate that with the intro-
duction of Al3+ ions, the short-range magnetic correlation
of Ca3CoMnO6 can be suppressed effectively and a more
robust long-range antiferromagnetic order is built.
2 Experiment
The Ca3CoMn1-xAlxO6 (x = 0, 0.05, 0.1, 0.15, 0.2) poly-
crystalline samples were prepared by a modified sol–gel
method [26]. Stoichiometric CaCO3 (99%, Aladdin),
C4H6MnO4·4H2O (99%, Aladdin), C16H36O4Ti (99%,
Aladdin), C4H6CoO4·4H2O (99.5%, Aladdin) and citric
acid (99%, Kermel) were dissolved into deionized water.
The fully mixed solution was heated in water bath for 12 h
and dried (150 °C) in oven for 5 h to obtain dried gel.
Subsequently, the obtained dried gel was ground and pre-
sintered at 800 °C for 24 h. After the mentioned processes,
the pre-sintered powder was reground and pressed into
cylindrical disks. Finally, the samples were sintered at
1000 °C for 10 h.
The structure of Ca3CoMn1-xAlxO6 (x = 0, 0.05, 0.1, 0.15,
0.2) samples was checked with Bruker D8 advanced X-ray
diffraction, which was equipped with Cu Ka radiation. The
scanning rate was 5°/min and the step size was 0.02°. The
Rietveld structural refinement was performed with General
Structure Analysis System program. Raman measurement
(Renishaw in Via) was done, where the used laser wave-
length and power were 532 nm and 50 mW, respectively.
The microtopography was characterized by field-emission
scanning electron microscopy (SEM-JSM-6490LV), while
magnetization measured by commercial physical property
measurement system (Quantum Design-Dyna Cool II).
3 Results and discussion
Figure 1 shows the XRD patterns and the calculated lattice
constants of the as-prepared Ca3CoMn1-xAlxO6 (x = 0, 0.05,
0.1, 0.15, 0.2) samples. For Fig. 1a–e, the spectra were
refined with R-3c space group. It was assumed that all the Co
ions were located in the trigonal prismatic sites and all the
Mn/Al ions occupied the octahedral sites. The calculated
parameters and Rwp, Rp, and χ2 values of the samples are
listed in Table 1. In this case it is noticed that a small dif-
ference between the measured intensity and the calculated
intensity of the spectra can be observed. If we assume that the
Co/Mn(Al) ions distribute randomly, a better fitting result can
be obtained. However, the complete random distribution is
incompatible with the dominant antiferromagnetic order.
665
This could be due to the existence of local anti-site disorder
of Co/Mn(Al) ions in some small nanoregions.
With introduction of Al3+ ions, both the lattice constants
a and c present a nonmonotonic variation (as shown in Fig.
1f), though very little. At low doping level, as the doping
content increases from 0 to 0.1, the a and c values decrease
slightly. As the doping content increases higher than x =
0.15, the Al3+ ions increase and the lattice parameters
become larger. This phenomenon can be explained properly.
As confirmed by the refined XRD spectra, local anti-site
disorder of Co/Mn(Al) ions exists in Ca3CoMn1-xAlxO6. The
entrance of Al3+ ions to the trigonal position leads to a
massive shrinkage of the octahedra. Such shrinkage reduces
the dimension of the lattice structure. In addition, the Al3+
ions located in the trigonal sub-lattice will have a low
coordination number, thus a smaller ionic radius which leads
to a decrease in volume of the trigonal sub-lattice. These two
mechanisms result in the reduction of the lattice parameters.
The Al3+ ions take the octahedral position, whose coordi-
nation number is 6. The ionic radius of Al3+ is slightly larger
than Mn4+. This makes the sub-lattice to expand. Finally, the
above combined effect leads to nonmonotonic variation of
the lattice parameters.
Figure 2a shows the Raman spectra of Ca3CoMn1-xAlxO6
(x = 0, 0.05, 0.1, 0.15, 0.2) samples. The wavelength of the
used laser was λ = 532 nm and the measuring wave number
ranged from 100 to 1000 cm−1. Comparing with x = 0 sam-
ple, no extra Raman peak emerged for the doped samples.
This is in accordance with the XRD results, and further
suggests the successful introduction of Al3+ ions. The sub-
stitution also causes the full width at half maximum increase,
implying a decreased crystallinity degree of the Al3+ doped
samples. The 125 cm−1 Raman mode corresponds to the
rotation of MnO6 octahedron, while 178 and 254 cm−1 to the
bending and stretching of Co–Mn bonds. Further, 194 and
291 cm−1 correspond to the stretching and bending of Ca–O
bonds, while 505 cm−1 to the bending of Mn–O bond.
Finally, 443, 540, 563, and 647 cm−1 Raman modes are
related to the anti-stretching of the MnO6 octahedron. The
increase of the relative intensity of the 540 cm−1 Raman
mode with increasing Al content can be attributed to the
substitution effect of the ions. As the Mn4+ ions are replaced
by Al3+ ions, the different valence state of Al3+ and Mn4+
changes the bonding of the atoms and causes the intensity of
the Raman peak to increase.
Figure 2b–f gives the morphology of Ca3CoMn1-xAlxO6
(x = 0, 0.05, 0.1, 0.15, 0.2) samples. The statistical size
distribution is shown in Fig. 3a–e and doping content
dependent particle size is depicted in Fig. 3f. It is noted that
with the introduction of Al3+ ions, the mean particle size
decreases from 1.15 to 0.37 μm by passing 1.08, 0.79, and
0.54 μm. This effect might be related with the bonding
energies. The bonding energy of Al–O bond is larger than
666
Fig. 1 a–e The refined XRD patterns of Ca3CoMn1-xAlxO6 (x = 0, 0.05, 0.1, 0.15, 0.2) samples: experimental value, calculated value, and
difference, f the Al3+ content dependent lattice parameters
the Mn–O bond. Introduction of Al3+ ions into Ca3CoMnO6
demands higher energy for the crystallization to take place,
hence reducing the size of the particle
Figure 4a–e shows the zero field cooling (ZFC) and field
cooling (FC) curves of Ca3CoMn1-xAlxO6(x = 0, 0.05, 0.1,
0.15, 0.2) samples measured in μ0H = 1000 Oe. For the
sample x = 0, a typical antiferromagnetic transition peak
exists in both the ZFC and FC curves around TN = 13 K. The
result is similar with the previous reports and corresponds to
the establishment of ↑↑↓↓ spin order of the Co-Mn-Co-Mn
chains [26]. In addition, due to the “order by disorder”
Journal of Sol-Gel Science and Technology (2021) 97:663–671
phenomenon, competing short-range antiferromagnetic and
ferromagnetic correlations form, a broad freezing peak also
appears in the ZFC curve of sample x = 0 in the high-
temperature region (100–150 K) together with a large
separation of the ZFC and FC curves. With increasing Al3+
content, the high-temperature freezing peak is suppressed.
For sample x = 0.05, only a kink exists while for sample
x = 0.1 the anomaly disappears and the curves become quite
smooth. Concurrently, the separation of ZFC and FC curves
weakens. For the sample x = 0.2 the curves superpose
completely.
Journal of Sol-Gel Science and Technology (2021) 97:663–671 667

Table 1 The calculated bond

x Bond distances (Å) Lattice parameters Rwp Rp χ2
distances, lattice constants, and
Rwp, Rp, and χ2 values for a (Å) c (Å) V (Å3)
Ca3CoMn1-xAlxO6 (x = 0, 0.05,
0.1, 0.15, 0.2) samples 0 Mn1-Co1 2.64447(33) × 2 9.12991 10.57789 763.594 3.98% 0.031 1.204
Mn1-O1 1.903(8) × 6
Co1-O1 2.175(8) × 6
0.05 Mn1-Co1 2.64302(19) × 2 9.12946 10.57213 763.103 4.74% 0.038 1.140
Mn1-O1 1.901(9) × 6
Co1-O1 2.132(10) × 6
0.1 Mn1-Co1 2.64166(30) × 2 9.12792 10.5663 762.450 4.61% 0.036 1.173
Mn1-O1 1.888(14) × 6
Co1-O1 2.251(15) × 6
0.15 Mn1-Co1 2.6420(6) × 2 9.12903 10.56809 762.739 4.26% 0.034 1.115
Mn1-O1 1.875(10) × 6
Co1-O1 2.201(11) × 6
0.2 Mn1-Co1 2.64236(24) × 2 9.13332 10.56944 763.554 4.37% 0.034 1.087
Mn1-O1 1.90457(13) × 6
Co1-O1 2.13939(14) × 6

Fig. 2 a The Raman spectra and

b–f the SEM images of
Ca3CoMn1-xAlxO6(x = 0, 0.05,
0.1, 0.15, 0.2) samples

To further investigate the influence of Al3+ dopant on the samples were measured at T = 75 K, the temperature is well
magnetic order of Ca3CoMnO6, the field-dependent mag- above the antiferromagnetic transition temperature TN but
netization of Ca3CoMn1-xAlxO6(x = 0, 0.05, 0.1, 0.15, 0.2) lower than the freezing temperature Tf. From Fig. 5a it can
668
Fig. 3 a–e The histogram of the
size distribution of Ca3CoMn1-x
AlxO6(x = 0, 0.05, 0.1, 0.15, 0.2)
samples, f the doping content
dependence of the particle size
be seen that there is a hysteresis loop for sample x = 0. With
increasing Al3+ content to x = 0.05, both the coercive field
(Hc) and remnant magnetization (Mr) decrease as shown in
Fig. 5b. This leads to a reduced area of the hysteresis loop.
For the three samples where x ≥ 0.1, the M-H curves become
almost linear. This result is in line with the temperature-
dependent magnetization curves, hence suggesting the
suppression effect of Al3+ ions to the high-temperature
short-range magnetic correlation.
In order to gain a deeper insight, the field-dependent
magnetization was measured a second time at T = 2 K with
a maximal field of Hmax = 9T. The curves are illustrated in
Fig. 6a. At low field, the magnetization increases linearly
with increasing field for all samples, indicating the domi-
nant antiferromagnetic interaction [27]. At high field, a
metamagnetic transition from ↑↑↓↓ magnetic order to ↑↑↓↑
Journal of Sol-Gel Science and Technology (2021) 97:663–671
magnetic order occurs, where the M-H curves display an
obvious hysteresis. Due to the dilution effect of non-
magnetic Al3+ ions, the magnetization decreases mono-
tonously as the Al3+ content increases. Figure 6b depicts
the first derivative of the M-H curves, where the transition
field corresponds to the spin flop of the field decreasing
branch defined as HSF and marked with the down arrows.
Except the sample x = 0.15, the transition field increases
generally, suggesting that the suppression effect of Al3+
ions to the short-range magnetic correlation helps in
establishing a more robust long-range antiferromagnetic
order. For the magnetic anomaly of the sample x = 0.15, it
may be relate to the structural anomaly since a subtle
structural change greatly affects the delicate competition
between the ionic (charge) order and spin frustration.24
With the introduction of Al3+ ions, below HSF several new
Journal of Sol-Gel Science and Technology (2021) 97:663–671
Fig. 4 a–e The ZFC and FC
curves of Ca3CoMn1-xAlxO6(x =
0, 0.05, 0.1, 0.15, 0.2) samples
measured in μ0H = 1000 Oe
Fig. 5 a The magnetic field-
dependent magnetization and
b the coercive field Hc and
remnant magnetization Mr of
Ca3CoMn1-xAlxO6(x = 0, 0.05,
0.1, 0.15, 0.2) samples measured
at T = 75 K
peaks also emerge in dM/dH curves for the three samples
x ≥ 0.1. The course for such result should be the replace-
ment of Mn4+ by Al3+ forms …Co2+-Mn4+-Co3+-Al3+…
ionic order in some small nanoregions and the ↑↑↓↓ long-
range order breaks. As a result, the correlation length
decreases, and the magnetic moment in these nanoregions
can be reversed by external field more easily.
To investigate the low-temperature dynamic behavior,
the time-dependent magnetization of the samples was
measured. Figure 7a shows the normalized magnetization
measured in zero field. In this case the samples were
cooled down to 5 K, a field of 5T was applied and kept for
10 min. The field was switched off and the remnant
magnetization was recorded. As Al3+ doping increases,
the short-range magnetic correlation can be driven more
easily by the use of thermal activation energy as mani-
fested by the faster and faster relaxation rate. This sug-
gests a reduced short-range magnetic correlation length in
669
Al3+-doped samples. Figure 7b shows the time-dependent
magnetization of three representative samples (x = 0,
0.05, 0.15) measured in a 5T field. In this case the samples
were first cooled down to 5 K and the magnetic field
switched on. When the field reached 5 T, the magnetiza-
tion was recorded immediately. In consistent with Fig. 7a,
the result shown in Fig. 7b confirms again the faster
relaxation found in Al3+ doped Ca3CoMn1-xAlxO6 sam-
ples. Unlike in Fig. 7a where the magnetization decreases
continuously, a striking nonmonotonic relaxation beha-
vior is observed in Fig. 7b. Similar phenomenon has also
happened in the isostructural Ca3Co2O6 and is ascribed to
the competition of two different relaxation mechanisms;
the quantum tunneling of magnetization and the thermally
activated relaxation process [28]. Therefore, the decrease
of magnetization in Fig. 7b may also imply the possible
existence of quantum tunneling of magnetization in
Ca3CoMn1-xAlxO6 samples [28–30].
670 Journal of Sol-Gel Science and Technology (2021) 97:663–671

Fig. 6 a The field-dependent

magnetization curves of
Ca3CoMn1-xAlxO6(x = 0, 0.05,
0.1, 0.15, 0.2) samples measured
at T = 2 K. b The dM/dH curves
for Ca3CoMn1-xAlxO6(x = 0,
0.05, 0.1, 0.15, 0.2) samples, for
comparing the curves are shifted
up by adding a constant value

Fig. 7 The normalized time-dependent M/M0 curves for Ca3CoMn1-x magnetization was recorded. b The magnetization was measured by
AlxO6(x = 0, 0.05, 0.1, 0.15, 0.2) measured at 5 K. a The magnetization cooling the samples down to 5 K firstly and the magnetic field was
was measured by cooling the samples down to 5 K, a field of 5T was switched on, as well as field reaches 5T the magnetization was recorded
applied and kept for 10 min, switching off the field and the remnant immediately

4 Conclusion Acknowledgements This work was supported by the key research

In conclusion, Ca3CoMn1-xAlxO6 (x = 0, 0.05, 0.1, 0.15, 0.2)
samples were synthesized and all of them crystallized into
single-phase rhombohedral structure. Due to the dilution effect
of the nonmagnetic Al3+ ions to the …Co2+-Mn4+-Co2+-
Mn4+…spin chains, the high-temperature spin freezing peak
disappears gradually and a faster dynamic behavior in the
doped samples is observed. Our investigation confirms that
the substitution of the nonmagnetic Al3+ ions has a similar
effect with the Co/Mn defection. This is to say that the non-
magnetic doping could also suppress the formation of short-
range magnetic correlation and help in building a more robust
long-range antiferromagnetic order. For the nonmonotonic
relaxation of the time-dependent magnetization, it implies the
possible existence of quantum tunneling of magnetization.
Data availability
project of colleges and universities of Henan province (20A140029,
16A140021), the Doctoral Fund Project of Zhengzhou University of
Light Industry (Grant no. 2015BSJJ069), and the National Science
Foundation of China (Grant nos. 61571403, 11604281).
Funding This work was supported by the Doctoral Fund Project of
Zhengzhou University of Light Industry (Grant no. 2015BSJJ069) and
the key research project of colleges and universities of Henan province
(20A140029, 16A140021), the National Science Foundation of China
(Grant no. 61571403, 11604281).
Author contributions YW and GG conceived, designed the study, and
edited the manuscript. Material preparation, data collection, and ana-
lysis were performed by JZ, CS, and HH. YS performed the structure
analysis. All authors read and approved the manuscript.
Compliance with ethical standards
Conflict of interest The authors declare that they have no conflict
of interest.

All data generated or analyzed during this study are inclu- Publisher’s note Springer Nature remains neutral with regard to
jurisdictional claims in published maps and institutional affiliations.
ded in this published article.
Journal of Sol-Gel Science and Technology (2021) 97:663–671
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