Ceramics International 45 (2019) 12022–12027

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Ceramics International
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Magnetic and impedance properties of magnetoelectric Co4Nb2O9 T

∗,1
Satish Yadav, Mohit Chandra, Kiran Singh
UGC-DAE Consortium for Scientific Research, University Campus, Khandwa Road, Indore, 452001, India

A R T I C LE I N FO A B S T R A C T

Keywords: The compound Co4Nb2O9 (CNO) exhibits interesting magnetoelectric coupling across its antiferromagnetic
C magnetic properties transition temperature (TN). Here, we report the structural, magnetic and complex dielectric properties of
C dielectric properties polycrystalline CNO within a wide temperature range (120–360 K), well above its TN. The temperature de-
C impedance pendent dc magnetization reveals that TN ∼27.2 K. The isothermal magnetization results infer the magnetic field
Magnetoelectric
induced transition around 11 kOe at 5 K. The temperature dependent real part of complex dielectric behavior
shows sharp increase around 160 K with frequency dispersion and a clear frequency dependent peak is observed
in tanδ across the same temperature region. This feature corroborates the dielectric relaxation in CNO well above
the long range magnetic ordering. Interestingly; the Curie-Weiss behavior of magnetization results deviate from
linearity around the same temperature regime (∼160 K) which suggests the presence of short range magnetic
correlation well above TN. The details impedance spectroscopy results are also analyzed to comprehend the grain
and grain boundary contributions.

1. Introduction sites. The magnetic structure of this compound is reported in different

reports with different interpretation and not understood very well.
The multiferroic materials with magnetoelectric (ME) coupling at- Earlier, Bertaut et al. [13] reported that it is linear in which the mo-
tracted enormous attention owing to both the fundamental physics and ments of two Co2+ ions are aligned opposite to each other and directed
promising applications in the next generation electronic devices such as along crystallographic c-axis. Khanh et al. [14] have shown that its
spintronic, multi-state memories, sensor etc. In ME materials magneti- magnetization and ME properties are not consistence with its linear
zation can be controlled by electric field and vice-versa. There are two magnetic structure and they suggested that its magnetic moments lie in
approaches to achieve ME coupling. First one is magnetism driven ab plane canted at an angle with c axis. In dielectric studies, most of the
ferroelectrics where magnetic and ferroelectric ordering appears at reports focused on the dielectric behavior near magnetic ordering [15]
same temperature; are highly demanding due to their outstanding ME and suggested that large ME coupling is the result of spin flop. Yiming
coupling e.g. TbMnO3 [1], R2Mn2O5 [2], GeV4S8 [3], Cr2O3 [4] and et al. [16] have shown that the ME coupling exists without spin flop and
other materials [5,6]. Second one is the composite multiferroics; where suggested the same even in the paraelectric state. This is only possible if
electric polarization and magnetization are coupled indirectly via strain there is existence of magnetic interactions above long range magnetic
e.g. BaTiO3eCoFe2O4 [7]. Besides these, there is another class of ma- ordering. Recently, Srivastava et al. [17] have shown the presence of
terials (sub-class of first one) in which electric polarization is developed spontaneous electric polarization in CNO even in the absence of mag-
only in the presence of the external magnetic fields like MnTiO3 [8], netic field by performing temperature cycling below TN. Surprisingly, in
NdCrTiO5 [9] etc. The compound Co4Nb2O9 (CNO) belongs to this ca- most of the reports the Curie-Weiss law is fitted only below 150 K ex-
tegory and exhibit dielectric peak and electric polarization around an- cept in Ref. [18] and similarly the dielectric behavior is reported near
tiferromagnetic transitions (TN) only in the presence of certain mag- the magnetic ordering except one report [10]. Hence, it is worth ex-
netic field [10]. The effect of electric field on the magnetic properties of ploring the magnetic and dielectric properties of this material at wide
CNO was firstly observed by Fischer et al., in 1972 [11]. temperature range.
The compound CNO crystallizes in Al2O3 type trigonal structure There are no detailed studies which describe the dielectric behavior
with space group P3̄ c1 [12]. The Co and Nb ions are occupying the Al of this material at wide temperature range. The complex dielectric
sites of Al2O3 structure in 2:1 ratio and Co ions have two non-equivalent behavior is useful technique to explore the relaxation, conduction

∗
Corresponding author.
E-mail addresses: [email protected], [email protected] (K. Singh).
1
Present Address: Department of Physics, Dr. B. R. Ambedkar National Institute of Technology, Jalandhar-144011, India.

https://doi.org/10.1016/j.ceramint.2019.03.096
Received 31 January 2019; Received in revised form 11 March 2019; Accepted 14 March 2019
Available online 16 March 2019
0272-8842/ © 2019 Published by Elsevier Ltd.
S. Yadav, et al. Ceramics International 45 (2019) 12022–12027

Fig. 1. (a) Room temperature Rietveld refinement of XRD of polycrystalline Co4Nb2O9. (b) Three dimensional visualization of crystal structure at room temperature.

Fig. 3. Temperature dependent (a) ε′ and (b) tanδ at different frequencies

during warming, inset in (b) shows Arrhenius fitting of tanδ peak.

Fig. 2. (a) Temperature dependent dc magnetization of Co4Nb2O9, inset shows

Curie-Weiss fitting (b) Isothermal magnetization at 5 K, inset shows dM/dH vs
H at 5 K.

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mechanism and different contributions in dielectric behavior. Our

temperature dependent (120–360 K) dielectric results at different fre-
quencies show the relaxation behavior which could be associated with
the magnetic short range correlation above TN. The contributions of
grain and grain boundary at higher temperatures are also discussed
using comprehensive studies on impedance spectroscopy.

2. Experimental techniques

The polycrystalline sample of CNO was prepared by conventional

solid-state reaction method using Co3O4 and Nb2O5 as starting in-
gredients. The stoichiometric powders were thoroughly ground using
mortar pestle and calcined at 1000 °C for 6 h. After calcination, the
powder was reground for 6 h and pressed to make pellets of 8 mm
diameter having thickness around 1–2 mm and sintered at 1100 °C for
6 h. The powder X-ray diffraction (XRD) measurement at room tem-
perature is performed on D2 Phaser Desktop Bruker diffractometer with
Cu-Kα radiation of wavelength λ = 1.5406 Å. The XRD data is refined
using Fullprof software [19] to determine the purity of the samples. The
dc magnetization measurements were done on a 7 T Quantum Design
SQUID-VSM. The complex dielectric and impedance spectroscopy
measurements are performed using home-made insert and data acqui-
sition software made on LabVIEW platform, coupled with Keysight LCR
meter model E4980A, in the temperature range 120–360 K and fre-
quency range 0.5 kHz–100 kHz. The isothermal complex dielectric
measurements are performed at different temperatures at wide fre-
quency range (20 Hz–1 MHz).

3. Results and discussion

The room temperature XRD data of the polycrystalline CNO with

Rietveld refinement is shown in Fig. 1(a). The XRD data is refined using
trigonal symmetry with space group P3̄ c1. The Rietveld refinement
confirms that prepared sample is single phase and the refined lattice
parameters are a = b = 5.1708 (1) Å and c = 14.1365 (7) Å which are
Fig. 4. Isothermal frequency dependent (a) ε′ and (b) tanδ at different tem- consistent with earlier reports [12–17]. The three dimensional visua-
peratures. lization of crystal structure is generated using VESTA software [20] and
shown in Fig. 1(b).
The temperature dependent dc magnetization (M-T) of CNO is

Fig. 5. Isothermal frequency dependent real (Z′) and imaginary part (Z″) of impedance spectroscopy at different temperatures.

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Fig. 6. Nyquist plots at some selected temperatures, the arrows indicate the increase direction of frequency.

measured at 500 Oe. Fig. 2(a) shows the temperature dependent zero of magnetization is different. This feature demostrates that at this
field cooled (zfc) curve. This figure clearly demonstrates the appear- temperature CNO undergoes magnetic field induced transition. The
ance of peak around 27.2 K which is associated to its TN. The TN value is critical magnetic field is around 11 kOe which can be seen from the first
same as reported by Kolodiazhnyi et al. [10] which support the good derivative of M − H curve in the inset of Fig. 2(b). The value of this
quality of the prepared sample. The Curie-Weiss fitting of magnetiza- critical magnetic field is consistent with previous work [10]. This is the
tion from 300 K is shown in the inset in Fig. 2(a). In most of the studies, field above which the peak is observed in the dielectric constant at TN
the Curie-Weiss fitting is done only below 120 K and hence the higher [15].
value of μeff. We have fitted the data from room temperature and found The temperature dependent real part of dielectric constant (ε′) and
that it is not obeying Curie-Weiss behavior till TN as reported in other dielectric loss (tanδ) at different frequencies is presented in Fig. 3(a)
reports [10]. However, the Curie-Weiss fitting is valid only above and (b), respectively. The ε′ vs temperature plot shows that up to 150 K
150 K, see the inset of Fig. 2 (a). The Curie-Weiss fitting yields the there is almost no frequency dispersion and ε′ value is less than 20.
θw = −52.23 K and μeff = 1.53 μB per Co ion. Moreover, the magneti- Above 150 K, ε′ increases sharply and have frequency dispersion. A
zation and thermal expansion results show anisotropic behavior along clear frequency dependent peak and dispersion can be seen in tanδ vs
[110] and [100] directions even much above TN (till 100 K) [15]; this temperature curves in Fig. 3(b). The peak position in tanδ shifted to-
suggests that there is some short range magnetic correlations due to wards higher temperature with increasing the measurement frequency.
anisotropic magnetic properties or local structural disorder even higher This type of relaxation is observed in relaxor ferroelectrics [24–26].
than TN. The spin chain system Ca3Co2O6 also infers short range cor- These results illustrate the dielectric relaxation in CNO at wide tem-
relation well above the long range magnetic ordering [21–23]. perature range (160–280 K); at much higher temperature than TN. In-
The isothermal magnetization (M − H) at 5 K is shown in Fig. 2(b). terestingly, the value of tanδ is also small up to 300 K and then started
This figure shows that there exists a critical field above which the slope increasing sharply. The sharp increase in tanδ above 300 K can be

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related to the increase in the dc conductivity of CNO which we will 4. Conclusions

discuss in impedance results in the coming section. This feature is dif-
ferent as reported by Kolodiazhnyi et al. [10] and the value of tanδ is In summary, the compressive magnetic and dielectric studies have
also less which shows the better insulating behavior of our sample. The been accomplished to understand the magnetic and dielectric behavior
similar dielectric relaxation is also observed in other magnetic system of polycrystalline CNO. The magnetization measurement shows an an-
[27,28]. The origin of this behavior is not very clear at this moment but tiferromagnetic ordering around 27.2 K and a magnetic field induced
it seems that it could be due to short range magnetic correlations or transition at 5 K with critical magnetic field around 11 kOe. The Curie-
local structural distortion well above TN as reported in CaCu3Ti4O12 Weiss law obeys above 150 K which indicates that some short range
[28] and Ca3Co2O6 [21]. Our Curie-Weiss fitting on magnetization re- magnetic correlations persist well above TN. The dielectric relaxation is
sults also shows the deviation from linear behavior around same tem- observed from 150 to 280 K and follows Arrhenius behavior. The im-
perature. The maxima in tanδ (peak temperature) are analyzed using pedance spectroscopy study confirms that the grain contribution dom-
Arrhenius equation. inates the dielectric behavior below 325 K. The relaxation behavior in
dielectric may arise due to the short range magnetic correlations or
f = f0 [exp (-Ea/KBT)] (1)
structural distortion around this temperature regime. Further studies
where f0 is the pre-exponential term, Ea is the activation energy and KB are requisite to prove the presence of short range magnetic correlations
is the Boltzmann constant. The linear fitting of Arrhenius equation is or structural distortion around the relaxation regime.
shown in the inset of Fig. 3(b) and the activation energy of this re-
laxation is 0.326 ± 0.001 eV. Further studies are required to prove the Acknowledgements
presence of short range magnetic correlations or structural distortion
using local measurement tools like Raman spectroscopy [29,30]. We would like to thank Dr. D. M. Phase for XRD measurement, Dr.
The isothermal frequency dependent ε′ and tanδ are shown in R. J. Choudhary for magnetization measurements and Dr. R. Rawat for
Fig. 4(a) and (b), respectively. One can clearly observe a broad peak in his support in experimentation and discussion.
tanδ which is shifted to higher frequency with increasing temperature.
The value of the tanδ increases slightly with increasing temperature. References
The relaxation frequency (peak frequency) increases with increasing
temperature and peak width decreases with increasing temperature. [1] T. Kimura, T. Goto, H. Shintani, K. Ishizaka, T. Arima, Y. Tokura, Magnetic control
of ferroelectric polarization, Nature 426 (2003) 55–58.
The relaxation behavior is explained in temperature dependent di-
[2] N. Hur, S. Park, P.A. Sharma, J.S. Ahn, S. Guha, S.W. Cheong, Electric polarization
electric measurement (Fig. 2) which could be due to the short range reversal and memory in a multiferroic material induced by magnetic fields, Nature
magnetic correlations or structural distortion above TN. Besides this 429 (2004) 392–395.
[3] K. Singh, C. Simon, E. Cannuccia, M.B. Lepetit, B. Corraze, E. Janod, L. Cario,
there is another small hump in tanδ at lower frequency, which is also
Orbital-ordering-driven multiferroicity and magnetoelectric coupling in GeV4S8,
shifted to higher frequency with increasing temperature. Phys. Rev. Lett. 113 (2014) 137602.
To understand the contributions of grain and grain boundary in [4] A. Iyama, T. Kimura, Magnetoelectric hysteresis loops in Cr2O3 at room tempera-
impedance results, we have analyzed the complex impedance spectro- ture, Phys. Rev. B 87 (2013) 180408.
[5] D. Khomskii, Trend: classifying multiferroics: mechanisms and effects, Physics 2
scopy at different temperatures. The real and imaginary part of the (2009) 20.
complex impedance Z ∗ = Z ′ + iZ ′′ is calculated using ε′ and ε″ from the [6] M. Chandra, S. Yadav, R.J. Choudhary, R. Rawat, A.K. Sinha, M.B. Lepetit, K. Singh,
following equation Multiferroicity and magnetoelastic coupling in α-Mn2O3: a binary perovskite, Phys.
Rev. B 98 (2018) 104427.
[7] C. Nan, L. Liu, N. Cai, J. Zha, Y. Ye, Y.H. Lin, L.J. Dong, C.X. Xiong, A three-phase
1 ε′ 1 ε′ ′ magnetoelectric composite of piezoelectric ceramics, rare-earth iron alloys, and
Z′ = 2 ′ 2
and Z ’ = polymer, Appl. Phys. Lett. 81 (2002) 3831–3833.
2πfC0 (ε′ + ε′ ) 2πfC0 (ε′ + ε′ ′ 2)
2
(2)
[8] N. Mufti, G.R. Blake, M. Mostovoy, S. Riyadi, A.A. Nugroho, T.M. Palstra,
Magnetoelectric coupling in MnTiO3, Phys. Rev. B 83 (2011) 104416.
where f is the frequency, C0 is the capacitance in the absence of di- [9] J. Hwang, E.S. Choi, H.D. Zhou, J. Lu, P. Schlottmann, Magnetoelectric effect in
electric medium. Fig. 5(a) and (b) show the frequency dependent real NdCrTiO5, Phys. Rev. B 85 (2012) 024415.
[10] T. Kolodiazhnyi, H. Sakurai, N. Vittayakorn, Spin-flop driven magneto-dielectric
and imaginary part of complex impedance at different temperatures. effect in Co4Nb2O9, Appl. Phys. Lett. 99 (2011) 132906.
This figure shows that impedance of CNO decreases with increasing [11] E. Fischer, G. Gorodetsky, R.M. Hornreich, A new family of magnetoelectric ma-
temperature which shows the semiconducting behavior of the studied terials: a2M4O9 (A Ta, Nb; M Mn, Co), Solid State Commun. 10 (1972) 1127–1132.
[12] Y. Fang, Y. Fang, Y. Song, W. Zhou, R. Zhao, R. Tang, H. Yang, L. Lv, S. Yang,
sample. The Nyquist plot (real and imaginary part of impedance) is D. Wang, Y. Du, Large magnetoelectric coupling in Co4Nb2O9, Sci. Rep. 4 (2014)
useful to understand the different contributions in impedance results of 3860.
polycrystalline materials like grain and grain boundary contributions. [13] E.F. Bertaut, L. Corliss, F. Forrat, R. Aleonard, R. Pauthenet, Etude de niobates et
tantalates de metaux de transition bivalents, J. Phys. Chem. Solids 21 (1961)
The grain and grain boundary contribution depends on sample pre-
234–251.
paration, temperature and the measurement frequencies. In general, the [14] N.D. Khanh, N. Abe, H. Sagayama, A. Nakao, T. Hanashima, R. Kiyanagi,
grain boundary contributions appear at lower frequencies whereas Y. Tokunaga, T. Arima, Magnetoelectric coupling in the honeycomb antiferro-
magnet Co4Nb2O9, Phys. Rev. B 93 (2016) 075117.
grain contribution dominating at higher frequencies. Fig. 6 shows the
[15] L.H. Yin, Y.M. Zou, J. Yang, J.M. Dai, W.H. Song, X.B. Zhu, Y.P. Sun, Colossal
Nyquist plots at some selected temperatures to understand the grain magnetodielectric effect and spin flop in magnetoelectric Co4Nb2O9 crystal, Appl.
and grain boundary contributions. Below 325 K, the Nyquist plots elu- Phys. Lett. 109 (2016) 032905.
cidate only one semicircle which infers the grain contributions to im- [16] Y. Cao, G. Deng, P. Beran, Z. Feng, B. Kang, J. Zhang, N. Guiblin, B. Dkhil, W. Ren,
S. Cao, Nonlinear magnetoelectric effect in paraelectric state of Co4Nb2O9 single
pedance results. The second semicircles which corresponds to grain crystal, Sci. Rep. 7 (2017) 14079.
boundary contribution, just appears at low frequency (31 Hz) at 325 K, [17] P. Srivastava, S. Chaudhary, V. Maurya, J. Saha, S. Kaushik, V. Siruguri, S. Patnaik,
whereas it is clearly visible at 360 K. From these plots, it is clear that the Magnetic structure driven ferroelectricity and large magnetoelectric coupling in
antiferromagnet Co4Nb2O9, Solid State Commun. 273 (2018) 39–43.
frequency which distinguishes the grain and grain boundary contribu- [18] C. Dhanasekhar, S.K. Mishra, R. Rawat, A.K. Das, A. Venimadhav, Coexistence of
tions increases with increasing temperature. For example at 325 K, the weak ferromagnetism with magnetoelectric coupling in Fe substituted Co4Nb2O9, J.
grain boundary contributions dominant below 31 Hz where is it is Alloy. Comp. 726 (2017) 148–153.
[19] J. Rodríquez-Carvajal, T. Roisnel, FullProf.98 and WinPLOTR: New Windows 95/
dominant till 178 Hz at 360 K. Fig. 6 also illustrates that the grain and NT Applications for Diffraction Commission for Powder Diffraction, International
grain boundary resistance decreases with increasing temperature which Union for Crystallography, Newletter No, (1998).
shows negative temperature coefficient of resistance. [20] K. Momma, F. Izumi, VESTA 3 for three-dimensional visualization of crystal, vo-
lumetric and morphology data, J. Appl. Cryst. 44 (2011) 1272–1276.
[21] R. Bindu, K. Maiti, S. Khalid, E.V. Sampathkumaran, Structural link to precursor

12026
S. Yadav, et al. Ceramics International 45 (2019) 12022–12027

effects, Phys. Rev. B 79 (2009) 094103. [27] S. Sharma, T. Basu, A. Shahee, K. Singh, N. Lalla, E. Sampathkumaran, Complex
[22] T. Basu, K.K. Iyer, K. Singh, E.V. Sampathkumaran, Novel dielectric anomalies due dielectric and impedance behavior of magnetoelectric Fe2TiO5, J. Alloy. Comp. 663
to spin-chains above and below Néel temperature in Ca3Co2O6, Sci. Rep. 3 (2013) (2016) 289–294.
3104. [28] A.M. Awasthi, J. Kumar, Discovery of strange kinetics in bulk material: correlated
[23] E.V. Sampathkumaran, P.L. Paulose, Spin-chain magnetism in Eu-doped Ca3Co2O6 dipoles in CaCu3Ti4O12, J. Appl. Phys. 112 (2012) 054108.
and Ca3CoRhO6 investigated by Mössbauer spectroscopy, Phys. Rev. B 77 (2008) [29] B.N. Rao, R. Datta, S.S. Chandrashekaran, D.K. Mishra, V. Sathe, A. Senyshyn,
172403. R. Ranjan, Local structural disorder and its influence on the average global structure
[24] L.E. Cross, Relaxor ferroelectrics, Ferroelectrics 76 (1987) 241–267. and polar properties in Na0.5B0.5TiO3, Phys. Rev. B 88 (2013) 224103.
[25] G.A. Samara, E.L. Venturini, Ferroelectric/relaxor crossover in compositionally [30] D.K. Mishra, V.G. Sathe, Evidence of the Fano resonance in a temperature depen-
disordered perovskites, Phase Transit. 79 (2006) 21–40. dent Raman study of CaCu3Ti4O12 and SrCu3Ti4O12, J. Phys. Condens. Matter 24
[26] A.A. Bokov, Z. Ye, Recent progress in relaxor ferroelectrics with perovskite struc- (2012) 252202.
ture, J. Mater. Sci. 41 (2006) 31–52.

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