Influence of thermal treatment on the ionic valence and the magnetic structure of perovskite manganites La0.95Sr0.05MnO3

Wu Li-Qian; Qi Wei-Hua; Li Yu-Chen; Li Shi-Qiang; Li Zhuang-Zhi; Xue Li-Chao; Ge Xing-Shuo; Ding Li-Li

doi:10.7498/aps.65.027501

Abstract

In traditional views, the magnetic ordering of oxides may be explained using magnetic superexchange (SE) or double exchange (DE) interaction models. Both models are based on an assumption that the valences of all oxygen ions be -2. For example, both La and Mn in LaMnO3 are assumed to be trivalent, in which antiferromagnetic spin structure is explained using the SE interaction between Mn3+ cations mediated by oxygen anions. In La1-xSrxMnO3, there exists a part of Mn4+ cations with the content ratio of Mn4+/Mn3+ being x/(1-x), in which spin structure and electronic transport properties are explained by DE interaction. However, there is a part of monovalent oxygen ions existing in oxides. Cohen [Nature 358 136] has calculated the densities of states for valence electrons in the perovskite oxide BaTiO3 using density functional theory. Results indicate that the average valence of Ba is +2, being the same as that in the traditional one, but the average valences of Ti and O are +2.89 and -1.63 respectively, agreeing with the results obtained using ionicity investigation [Rev. Mod. Phys. 42 317] and X-ray photoelectron spectra (XPS) analysis, but different from the conventional results +4 and -2. In this paper, three samples with the nominal composition La0.95Sr0.05MnO3 are prepared by different thermal-treatments. Likewise, there are only Mn2+ and Mn3+ cations, but no Mn4+ cations in La0.95Sr0.05MnO3, a result obtained by XPS analysis, and the average valence of Mn in La0.95Sr0.05MnO3 samples increases with increaseing thermal-treatment. Although the crystal structures of the samples are the same, the magnetic moments per formula are obviously different. This magnetic structure cannot be explained using the conventional SE and DE interaction models. Using the O 2p itinerant electron model for spinel ferrites proposed recently by our group, we can explain this magnetic structure. The variation trend of the average valences of Mn cations calculated using the magnetic moments per formula of the samples at 10 K, is in accordance with the experiment results of XPS. The O 2p itinerant electron model is based on an assumption that there is a part of monovalent oxygen ions in the oxides, which is the fundamental difference from SE and DE interaction models.

Keywords:

Authors and contacts

1.
Hebei Advanced Thin Film Laboratory, Department of Physics, Hebei Normal University, Shijiazhuang 050024, China;
2.
No.46 Research Institute of China Electronics Technology Group Corporation, Tianjin 300220, China

Corresponding author: Xue Li-Chao, tanggd@mail.hebtu.edu.cn.

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 11174069), the Natural Science Foundation of Hebei Province, China (Grant No. A2015205111), and the Young Scholar Science Foundation of the Education Department of Hebei Province, China (Grant No. QN20131008).

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[24]	Wu L Q, Li Y C, Li S Q, Li Z Z, Tang G D, Qi W H, Xue L C, Ge X S, Ding L L 2015 AIP Advances 5 097210
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[26]	Thomas J, Pollini I 1985 Phys. Rev. B 32 2522
[27]	Chelikowsky J R, Burdett J K 1986 Phys. Rev. Lett. 56 961
[28]	Garca A, Cohen M L 1993 Phys. Rev. B 47 4215
[29]	Guo Y Y, Kuo C K, Nicholson P S 1999 Solid State Ionics 123 225
[30]	Liu S P, Tang G D, Hao P, Xu L Q, Zhang Y G, Qi W H, Zhao X, Hou D L, Chen W 2009 J. Appl. Phys. 105 013905
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[32]	Liu S P, Xie Y, Xie J, Tang G D 2011 J. Appl. Phys. 110 123714
[33]	Ji D H, Tang G D, Li Z Z, Han Q J, Hou X, Bian R R, Liu S R 2012 J. Appl. Phys. 111 113902
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[35]	Seah M P, Brown M T 1998 Journal of Electron Spectroscopy and Related Phenomena 95 71
[36]	Sunding M F Hadidi K, Diplas S, Lovvik O M, Norby T E, Gunns A E 2011 Journal of Electron Spectroscopy and Related Phenomena 184 399
[37]	Cui B, Lin H, Liu Y Z, Li J B, Sun P, Zhao X C, Liu C J 2009 J. Phys. Chem. C 113 14083
[38]	Zener C 1951 Phys. Rev. 82 403
[39]	Tang G D, Han Q J, Xu J, Ji D H, Qi W H, Li Z Z, Shang Z F, Zhang X Y 2014 Phys. B 438 91
[40]	Shang Z F, Qi W H, Ji D H, Xu J, Tang G D, Zhang X Y, Li Z Z, Lang L L 2014 Chin. Phys. B 23 107503
[41]	Lang L L, Xu J, Qi W H, Li Z Z, Tang G D, Shang Z F, Zhang X Y, Wu L Q, Xue L C 2014 J. Appl. Phys. 116 123901
[42]	Zhang X Y, Xu J, Li Z Z, Qi W H, Tang G D, Shang Z F, Ji D H, Lang L L 2014 Phys. B 446 92
[43]	Lang L L, Xu J, Li Z Z, Qi W H, Tang G D, Shang Z F, Zhang X Y, Wu L Q, Xue L C 2015 Phys. B 462 47
[44]	Xu J, Ji D H, Li Z Z, Qi W H, Tang G D, Zhang X Y, Shang Z F, Lang L L 2015 Physica Status Solidi B 252 411
[45]	Xu J, Qi W H, Ji D H, Li Z Z, Tang G D, Zhang X Y, Shang Z F, Lang L L 2015 Acta Phys. Sin. 64 017501 (in Chinese) [徐静, 齐伟华, 纪登辉, 李壮志, 唐贵德, 张晓云, 尚志丰, 朗莉莉 2015 64 017501]
[46]	Xu J, Ma L, Li Z Z, Lang L L, Qi W H, Tang G D, Wu L Q, Xue L C, Wu G H 2015 Physica Status Solidi B 252 2820
[47]	Chen C W 1977 Magnetism, Metallurgy of soft magnetic materials (North- Holland Publishing Company, 1977)
[48]	Lee H S, Park C S, Park H H 2014 Appl. Phys. Lett. 104 191604

Cited By

[1]	Helmolt R V, Wecker J, Holzapfel B, Schultz L, Samwer K 1993 Phys. Rev. Lett. 71 2331
[2]	Urushibara A, Moritomo Y, Arima T, Asamitsu A, Kido G, Tokura Y 1995 Phys. Rev. B 51 14103
[3]	Tokura Y, Tomioka Y 1999 J. Magn. Magn. Mater. 200 1
[4]	Salamon M B, Jaime M 2001 Rev. Moder. Phys. 73 583
[5]	Sun Y, Tong W, Xu X J, Zhang Y H 2001 Appl. Phys. Lett. 78 643
[6]	Lu Y, Li Q A, Di N L, Li R W, Ma X, Kou Z Q, Cheng Z H 2003 Chin. Phys. 12 1301
[7]	Tang G D, Hou D L, Chen W, Zhao X, Qi W H 2007 Appl. Phys. Lett. 90 144101
[8]	Tang G D, Hou D L, Li Z Z, Zhao X, Qi W H, Liu S P, Zhao F W 2006 Appl. Phys. Lett. 89 261919
[9]	Tang G D, Hou D L, Chen W, Hao P, Liu G H, Liu S P, Zhang X L, Xu L Q 2007 Appl. Phys. Lett. 91 152503
[10]	Tang G D, Liu S P, Zhao X, Zhang Y G, Ji D H, Li Y F, Qi W H, Chen W, Hou D L 2009 Appl. Phys. Lett. 95 121906
[11]	Liu S P, Tang G D, Li Z Z, Qi W H, Ji D H, Li Y F, Chen W, Hou D L 2011 J. Alloy Comp. 509 2320
[12]	Jiang K, Gong S K 2009 Chin.Phys.B 18 3035
[13]	Hu L, Sun Y P, Wang B, Luo X, Sheng Z G, Zhu X B, Song W H, Yang Z R, Dai J M 2010 Chin. Phys. Lett. 27 097504
[14]	Hong F, Cheng Z X, Wang J L, Wang X L, Dou S X 2012 Appl. Phys. Lett. 101 102411
[15]	Liu N, Yan G Q, Zhu G, Guo H Y 2012 Rare Metals 31 135
[16]	Yang H, Qi W H, Ji D H, Shang Z F, Zhang X Y, Xu J, Lang L L, Tang G D 2014 Acta Phys. Sin. 63 087503 (in Chinese) [杨虹, 齐伟华, 纪登辉, 尚志丰, 张晓云, 徐静, 郎莉莉, 唐贵德 2014 63 087503]
[17]	Khan M H, Pal S, Bose E 2015 J. Magn. Magn. Mater. 391 140
[18]	Jiang L N, Zhang Y B, Dong S L 2015 Acta Phys. Sin. 64 147104 (in Chinese) [姜丽娜, 张玉滨, 董顺乐 2015 64 147104]
[19]	Jonker G H, Van Santen J H 1950 Physica 16 337
[20]	Shannon R D 1976 Acta Cryst. A 32 751
[21]	Chikazumi S 1997 Physics of Ferromagnetism 2e (Oxford University Press), p100-180
[22]	Cohen R E 1992 Nature 358 136
[23]	Dupin J C, Gonbeau D, Vinatier P, Levasseur A 2000 Phys. Chem. Chem. Phys. 2 1319
[24]	Wu L Q, Li Y C, Li S Q, Li Z Z, Tang G D, Qi W H, Xue L C, Ge X S, Ding L L 2015 AIP Advances 5 097210
[25]	Phillips J C 1970 Rev. Mod. Phys. 42 317
[26]	Thomas J, Pollini I 1985 Phys. Rev. B 32 2522
[27]	Chelikowsky J R, Burdett J K 1986 Phys. Rev. Lett. 56 961
[28]	Garca A, Cohen M L 1993 Phys. Rev. B 47 4215
[29]	Guo Y Y, Kuo C K, Nicholson P S 1999 Solid State Ionics 123 225
[30]	Liu S P, Tang G D, Hao P, Xu L Q, Zhang Y G, Qi W H, Zhao X, Hou D L, Chen W 2009 J. Appl. Phys. 105 013905
[31]	Liu S P, Zhang Y G, Tang G D, Qi W H, Ji D H, Li Y F, Liu G H, Xie Y, Chen W, Hou D L 2010 Phys. Stat. Sol. 207 2437
[32]	Liu S P, Xie Y, Xie J, Tang G D 2011 J. Appl. Phys. 110 123714
[33]	Ji D H, Tang G D, Li Z Z, Han Q J, Hou X, Bian R R, Liu S R 2012 J. Appl. Phys. 111 113902
[34]	Liu S P, Xie Y, Tang G D, Li Z Z, Ji D H, Li Y F, Hou D L 2012 J. Magn.Magn.Mater. 324 1992
[35]	Seah M P, Brown M T 1998 Journal of Electron Spectroscopy and Related Phenomena 95 71
[36]	Sunding M F Hadidi K, Diplas S, Lovvik O M, Norby T E, Gunns A E 2011 Journal of Electron Spectroscopy and Related Phenomena 184 399
[37]	Cui B, Lin H, Liu Y Z, Li J B, Sun P, Zhao X C, Liu C J 2009 J. Phys. Chem. C 113 14083
[38]	Zener C 1951 Phys. Rev. 82 403
[39]	Tang G D, Han Q J, Xu J, Ji D H, Qi W H, Li Z Z, Shang Z F, Zhang X Y 2014 Phys. B 438 91
[40]	Shang Z F, Qi W H, Ji D H, Xu J, Tang G D, Zhang X Y, Li Z Z, Lang L L 2014 Chin. Phys. B 23 107503
[41]	Lang L L, Xu J, Qi W H, Li Z Z, Tang G D, Shang Z F, Zhang X Y, Wu L Q, Xue L C 2014 J. Appl. Phys. 116 123901
[42]	Zhang X Y, Xu J, Li Z Z, Qi W H, Tang G D, Shang Z F, Ji D H, Lang L L 2014 Phys. B 446 92
[43]	Lang L L, Xu J, Li Z Z, Qi W H, Tang G D, Shang Z F, Zhang X Y, Wu L Q, Xue L C 2015 Phys. B 462 47
[44]	Xu J, Ji D H, Li Z Z, Qi W H, Tang G D, Zhang X Y, Shang Z F, Lang L L 2015 Physica Status Solidi B 252 411
[45]	Xu J, Qi W H, Ji D H, Li Z Z, Tang G D, Zhang X Y, Shang Z F, Lang L L 2015 Acta Phys. Sin. 64 017501 (in Chinese) [徐静, 齐伟华, 纪登辉, 李壮志, 唐贵德, 张晓云, 尚志丰, 朗莉莉 2015 64 017501]
[46]	Xu J, Ma L, Li Z Z, Lang L L, Qi W H, Tang G D, Wu L Q, Xue L C, Wu G H 2015 Physica Status Solidi B 252 2820
[47]	Chen C W 1977 Magnetism, Metallurgy of soft magnetic materials (North- Holland Publishing Company, 1977)
[48]	Lee H S, Park C S, Park H H 2014 Appl. Phys. Lett. 104 191604

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