Enhanced low-field magnetocaloric effect in Nb and Al co-substituted EuTiO3 compounds

doi:10.1016/j.jmst.2022.02.005

Abstract

Abstract:

The magnetic ground state switching between antiferromagnetic (AFM) and ferromagnetic (FM) states in EuTiO₃ provides the feasibility of regulating its magnetic properties and magnetocaloric effect. First-principles calculations demonstrate that the magnetic ground states for EuTi_0.875Nb_0.0625Al_0.0625O₃, EuTi_0.8125Nb_0.125Al_0.0625O₃, and EuTi_0.75Nb_0.125Al_0.125O₃ are FM coupling. Experimental results also exhibit the FM coupling domination in these compounds, accompanied by a significantly enhanced low magnetic field magnetocaloric effect. The maximum magnetic entropy change of all the samples surpasses 15 J kg^-1 K^-1 with a field change of 1 T, which is 1.4 times as large as that of bulk EuTiO₃. Especially, the maximum refrigerating capacity for EuTi_0.8125Nb_0.125Al_0.0625O₃ compound is evaluated to be 88.1 J kg^-1, more than three times of that of EuTiO₃. The remarkable magnetocaloric performances prove Nb and Al co-substituted EuTiO₃ compounds to be competitive candidates for magnetic refrigeration in the liquid helium temperature regime.

Key words: Magnetocaloric effect, Europium titanate (EuTiO₃), Ferromagnetic, Magnetic refrigeration

Huicai Xie, Wenxia Su, Haiming Lu, Zhaojun Mo, Dunhui Wang, Hao Sun, Lu tian, Xinqiang Gao, Zhenxing Li, Jun Shen. Enhanced low-field magnetocaloric effect in Nb and Al co-substituted EuTiO₃ compounds[J]. J. Mater. Sci. Technol., 2022, 118: 128-135.

Figures/Tables 9

Table 1. The single point energies of FM and G-AFM states for EuTi0.875Nb0.0625Al0.0625O3, EuTi0.8125Nb0.125Al0.0625O3, and EuTi0.75Nb0.125Al0.125O3.

Compounds	CalculatedE_FM (eV)	Calculated E_AFM (eV)
EuTi_0.875Nb_0.0625Al_0.0625O₃	-807.4973	-807.4012
EuTi_0.8125Nb_0.125Al_0.0625O₃	-809.3939	-808.5957
EuTi_0.75Nb_0.125Al_0.125O₃	-403.4682	-403.4454

Fig. 1. The DOS (left) and PDOS (right) for (a) EuTi0.875Nb0.0625Al0.0625O3, (b) EuTi0.8125Nb0.125Al0.0625O3, and (c) EuTi0.75Nb0.125Al0.125O3.

Fig. 2. Room temperature XRD patterns and Rietveld refinement curves of (a) EuTi0.875Nb0.0625Al0.0625O3, (b) EuTi0.8125Nb0.125Al0.0625O3, (c) EuTi0.75Nb0.125Al0.125O3 compounds, and (d) the simulated crystal structure.

Table 2. The crystallographic parameters obtained from the Rietveld refinements for the EuTi0.875Nb0.0625Al0.0625O3, EuTi0.8125Nb0.125Al0.0625O3, and EuTi0.75Nb0.125Al0.125O3 compounds.

Samples	A (Å)	R_p (%)	R_wp (%)	χ² (%)
EuTi_0.875Nb_0.0625Al_0.0625O₃	3.9070(5)	4.10	5.66	2.54
EuTi_0.8125Nb_0.125Al_0.0625O₃	3.9181(9)	4.83	7.34	5.13
EuTi_0.75Nb_0.125Al_0.125O₃	3.9145(9)	4.67	7.36	5.21

Fig. 3. ZFC and FC curves for (a) EuTi0.875Nb0.0625Al0.0625O3, (b) EuTi0.8125Nb0.125Al0.0625O3, (c) EuTi0.75Nb0.125Al0.125O3 compounds measured from 2 to 300 K in a field of 100 Oe, and (d) the first derivative of the ZFC curves between 2 and 30 K. Insets: the left indicates the ZFC and FC curves between 2 and 15 K, the right indicates the ZFC inverse susceptibility χ-1(T) curves fitted to the Curie-Weiss law.

Fig. 4. Isothermal M(H) curves measured in fields from 0 to 5 T at selected temperatures for (a) EuTi0.875Nb0.0625Al0.0625O3, (b) EuTi0.8125Nb0.125Al0.0625O3, (c) EuTi0.75Nb0.125Al0.125O3 compounds, and (d) the M(H) curves between 0 and 2 T at 2 K for the three compounds and EuTiO3.

Fig. 5. Temperature dependences of the -ΔSM under different magnetic field changes for (a) EuTi0.875Nb0.0625Al0.0625O3, (b) EuTi0.8125Nb0.125Al0.0625O3, (c) EuTi0.75Nb0.125Al0.125O3 compounds, and (d) the variation of RC value with magnetic field for the compounds and EuTiO3.

Fig. 6. Magnetocaloric parameters of the Nb and Al co-substituted compounds and some competitive magnetic refrigerants around liquid helium temperature.

Fig. 7. Magnetic field dependence of TEC(5) for the EuTi0.875Nb0.0625Al0.0625O3, EuTi0.8125Nb0.125Al0.0625O3, and EuTi0.75Nb0.125Al0.125O3 compounds.

References 48

[1]	L.W. Li, M. Yan, J. Alloy. Compd. 823 (2020) 153810. DOI URL
[2]	P. Mukherjee, S.E. Dutton, Adv. Funct. Mater. 27 (2017) 1701950. DOI URL
[3]	G.Z. Zhang, L.X. Weng, Z.Y. Hu, Y. Liu, R.X. Bao, P. Zhao, H. Feng, N. Yang, M.Y. Li, S.L. Zhang, S.L. Jiang, Q. Wang, Adv. Mater. 31 (2019) 1806642. DOI URL
[4]	R.V. Erp, R. Soleimanzadeh, L. Nela, G. Kampitsis, E. Matioli, Nature 585 (2020) 211-216. DOI URL
[5]	B. Yang, J.B. Trebbia, R. Baby, Ph. Tamarat, B. Lounis, Nat. Photonics 9 (2015) 658-662. DOI URL
[6]	G. Kawaguchi, A.A. Bardin, M. Suda, M. Uruichi, H.M. Yamamoto, Adv. Mater. 31 (2019) 1805715. DOI URL
[7]	A.Y. Vshivkov, A.V. Delkov, A.A. Kishkin, N.A. Lavrov, Chem. Pet. Eng. 55 (2019) 306-311. DOI URL
[8]	P. Jia, L.P. Duan, K. Wang, E.G. Wang, J. Mater. Sci. Technol. 35 (2019) 2283-2287. DOI URL
[9]	O. Tegus, E. Brück, K.H.J. Buschow, F.R. de Boer, Nature 415 (2002) 150-152. DOI URL
[10]	B.G. Shen, J.R. Sun, F.X. Hu, H.W. Zhang, Z.H. Cheng, Adv. Mater. 21 (2009) 4545-4564. DOI URL
[11]	Z.H. Dong, S. Huang, V. Ström, G. Chai, L.K. Varga, O. Eriksson, L. Vitos, J. Mater. Sci. Technol. 79 (2021) 15-20. DOI URL
[12]	Z.Q. Zhang, P.Y. Wang, H.W. Rong, L.W. Li, Dalton Trans. 48 (2019) 17792-17799. DOI URL
[13]	J.Z. Hao, F.X. Hu, H.B. Zhou, W.H. Liang, Z.B. Yu, F.R. Shen, Y.H. Gao, K.M. Qiao, J. Li, C. Zhang, B.J. Wang, J. Wang, J. He, J.R. Sun, B.G. Shen, Scr. Mater. 186 (2020) 84-88. DOI URL
[14]	Y.J. Wang, Y.S. Du, Y.Q. Zhang, L. Li, L. Ma, J. Wang, J.T. Zhao, G.H. Rao, Inter-metallics 127 (2020) 106989.
[15]	Z.Y. Li, F.F. Wang, P.Y. Zhu, D.Q. Wu, G.X. Cao, B. Zhai, Inorg. Chem. Commun. 120 (2020) 108166. DOI URL
[16]	Z.Q. Dong, S.H. Yin, Struct. Ceram. Int. 46 (2020) 1099-1103.
[17]	J. Brous, I. Fankuchen, E. Banks, Acta Crystallogr. 6 (1953) 67-70. DOI URL
[18]	M.W. Shafer, J. Appl. Phys. 36 (1965) 1145-1152. DOI URL
[19]	T.R. McGuire, M.W. Shafer, R.J. Joenk, H.A. Alperin, S.J. Pickart, J. Appl. Phys. 37 (1966) 981-982.
[20]	C.J. Fennie, K.M. Rabe, Phys. Rev. Lett. 97 (2006) 267602. DOI URL
[21]	T. Katsufuji, H. Takagi, Phys. Rev. B 64 (2001) 054415. DOI URL
[22]	J.H. Lee, L. Fang, E. Vlahos, X.L. Ke, Y.W. Jung, L.F. Kourkoutis, J.W. Kim, P.J. Ryan, T. Heeg, M. Roeckerath, V. Goian, M. Bernhagen, R. Uecker, P.C. Hammel, K.M. Rabe, S. Kamba, J. Schubert, J.W. Freeland, D.A. Muller, C.J. Fennie, P. Schiffer, V. Gopalan, E.J. Halperin, D.G. Schlom, Nature 466 (2010) 954-959. DOI URL
[23]	Z. Porter, R.F. Need, K. Ahadi, Y. Zhao, Z.J. Xu, B.J. Kirby, J.W. Lynn, S. Stemmer, S.D. Wilson, Phys. Rev. Mater. 4 (2020) 054411.
[24]	R. Das, R. Prabhu, N. Venkataramani, S. Prasad, L. Li, M.H. Phan, V. Keppens, D. Mandrus, H. Srikanth, J. Alloy. Compd. 850 (2021) 156819. DOI URL
[25]	Z.J. Mo, J. Shen, L. Li, Y. Liu, C.C. Tang, F.X. Hu, J.R. Sun, B.G. Shen, Mater. Lett. 158 (2015) 282-284. DOI URL
[26]	A. Midya, P. Mandal, K. Rubi, R.F. Chen, J.S. Wang, R. Mahendiran, G. Lorusso, M. Evangelisti, Phys. Rev. B 93 (2016) 094422. DOI URL
[27]	R. Ranjan, H.S. Nabi, R. Pentcheva, J. Phys. Condens. Matter 19 (2007) 406217. DOI URL
[28]	H. Akamatsu, Y. Kumagai, F. Oba, K. Fujita, H. Murakami, K. Tanaka, I. Tanaka, Phys. Rev. B 83 (2011) 214421. DOI URL
[29]	T. Wei, Q.G. Song, Q.J. Zhou, Z.P. Li, X.L. Qi, W.P. Liu, Y.R. Guo, J.M. Liu, Appl. Surf. Sci. 258 (2011) 599-603. DOI URL
[30]	W.H. Jiang, Z.J. Mo, J.W. Luo, Z.X. Zheng, Q.J. Lu, G.D. Liu, J. Shen, L. Li, Chin. Phys. B 29 (2020) 037502. DOI URL
[31]	W. Zhang, Z.J. Mo, W.H. Jiang, Z.H. Hao, J.W. Luo, R.J. Cheng, G.D. Liu, L. Li, J. Shen, J. Magn. Magn. Mater. 492 (2019) 165684. DOI URL
[32]	S. Zeng, W.H. Jiang, H. Yang, Z.J. Mo, J. Shen, L. Li, Chin. Phys. B 29 (2020) 127501. DOI URL
[33]	L. Li, H.D. Zhou, J.Q. Yan, D. Mandrus, V. Keppens, APL Mater. 2 (2014) 110701. DOI URL
[34]	R. Zhao, Y.D. Ji, C. Yang, W.W. Li, Y.Y. Zhu, W. Zhang, H. Lu, Y.C. Jiang, G.Z. Liu, J.W. Hong, H.Y. Wang, H. Yang, Ceram. Int. 46 (2020) 19990-19995. DOI URL
[35]	P.H.T. Philipsen, G. te Velde, E.J. Baerends, J.A. Berger, P.L. de Boeij, M. Franchini, J.A. Groeneveld, E.S. Kadantsev, R. Klooster, F. Kootstra, P. Romaniello, M. Raupach, D.G. Skachkov, J.G. Snijders, C.J.O. Verzijl, J.A. Celis Gil, J.M. Thijssen, G. Wiesenekker, T. Ziegler, BAND 2018, SCM, Theoretical Chemistry, Vrije Uni- versiteit, Amsterdam, The Netherlands, 2018 https://www.scm.com/product/band_periodicdft/.
[36]	G. Velde, E.J. Baerends, Phys. Rev. B 44 (1991) 7888-7903. PMID
[37]	J.P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 77 (1996) 3865-3868. DOI PMID
[38]	J. Head, P. Manuel, F. Orlandi, M. Jeong, M.R. Lees, R.K. Li, C. Greaves, Chem. Mater. 32 (2020) 10184-10199. DOI URL
[39]	V.K. Pecharsky, K.A. Gschneidner, J. Appl. Phys. 86 (1999) 565-575. DOI URL
[40]	Z.J. Mo, J. Shen, L.Q. Yan, J.F. Wu, L.C. Wang, Appl. Phys. Lett. 102 (2013) 192407. DOI URL
[41]	Y.Y. Yu, D.N. Petrov, K.C. Park, B.T. Huy, P.T. Long, J. Magn. Magn. Mater. 519 (2021) 167452. DOI URL
[42]	H. Zhang, C.F. Xing, H. Zhou, X.Q. Zheng, X.F. Miao, L.H. He, J. Chen, H.L. Lu, E.K. Liu, W.T. Han, H.G. Zhang, Y.X. Wang, Y. Long, L.V. Eijk, E. Brück, Acta Mater. 193 (2020) 210-220. DOI URL
[43]	J.W. Xu, X.Q. Zheng, S.X. Yang, L. Xi, J.Y. Zhang, Y.F. Wu, S.G. Wang, J. Liu, L.C. Wang, Z.Y. Xu, B.G. Shen, J. Alloy. Compd. 843 (2020) 155930. DOI URL
[44]	L.D. Griffith, Y. Mudryk, J. Slaughter, V.K. Pecharsky, J. Appl. Phys. 123 (2018) 034902. DOI URL
[45]	Z.Q. Zhang, P.Y. Wang, N. Wang, X.J. Wang, P. Xu, L.W. Li, Dalton Trans. 49 (2020) 8764-8773. DOI URL
[46]	D. Guo, Y.K. Zhang, B.B. Wu, H.F. Wang, R.G. Guan, X. Li, Z.M. Ren, J. Alloy. Compd. 830 (2020) 154666. DOI URL
[47]	B.B. Wu, D. Guo, Y.M. Wang, Y.K. Zhang, Ceram. Int. 46 (2020) 11988-11993. DOI URL
[48]	L.W. Li, P. Xu, S.K. Ye, Y. Li, G.D. Liu, D.X. Huo, M. Yan, Acta Mater. 194 (2020) 354-365. DOI URL

Enhanced low-field magnetocaloric effect in Nb and Al co-substituted EuTiO₃ compounds

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