Mn掺杂锶铁氧体SrFe12O19电子结构及磁性的第一性原理研究

doi:10.15541/jim20190003

摘要/Abstract

摘要：

为了揭示掺杂离子对具有磁铅石构型的锶铁氧体材料磁性能的影响, 本研究探讨了锶铁氧体及其锰掺杂体系的稳定构型及其磁结构。研究结果表明, 锶铁氧体为亚铁磁性, 与前期的研究结果相吻合。通过比较GGA和GGA+U计算方法, 发现U值的选取对体系的电子结构和原子磁矩有显著影响。当U值为3.7 eV时, 体系由金属性转变为自旋向上带隙为1.71 eV的半导体。原胞总磁矩为40 μ_B。对于Mn替换掺杂的SrFe_12-_xMn_xO₁₉体系, 通过不同占据位能量比较, 当单个Mn原子替换(x=0.5)时, Mn离子优先占据Fe (12k)位置; 而当两个Mn原子替换Fe原子(x=1.0)时, 两个Mn分别占据Fe (12k)和Fe (2a)位置。Mn掺杂对锶铁氧体的结构影响较小, 但对于体系的总磁矩和电子结构有较明显的影响。在Mn含量x=0.5和x=1.0时, 自旋向上带隙值分别降低到0.85和0.59 eV, 原胞的总磁矩为39和38 μ_B。本研究可为实验研究提供理论指导。

关键词: 锶铁氧体, Mn掺杂, 第一性原理, 电子结构, 磁矩

Abstract:

To reveal influence of doping ions on the magnetic properties of strontium ferrite materials with magnetoplumbite configurations, we studied the stable configurations and magnetic structures of strontium ferrite with and without manganese doping. The results show that the strontium ferrite is ferrimagnetic, which is consistent with the previous reports. Comparing the GGA and GGA+U approaches, the U value exhibits a significant impact on the electronic structures and atomic magnetic moments. When 3.7 eV is adopted for U value, the system changed from a metal to a semiconductor with a spin up band gap of 1.71 eV. The total magnetic moment of the pure strontium ferrite is 40 μ_B. For the SrFe_12-_xMn_xO₁₉ system, the site preference of Mn substituting Fe is investigated with x=0.5 and x=1.0. When x = 0.5, the single doping Mn atom preferentially occupies the Fe (12k) site. For x=1.0, the two Mn atoms preferentially occupy the Fe (12k) and Fe (2a) sites, respectively. Doping Mn has little impact on the lattice structure of strontium ferrite, but have a significant effect on the total magnetic moments and electronic structures. When x=0.5 and x=1.0, the band gap values for spin up electrons reduced to 0.85 and 0.49 eV, and the total magnetic moments reduced to 39 and 38 μ_B, respectively. This study may provide a theoretical foundation for future experimental studies.

Key words: SrFe₁₂O₁₉, Mn-doped, the first principles, electronic structure, magnetic moment

中图分类号:

TQ174

王中, 查显弧, 吴泽, 黄庆, 都时禹. Mn掺杂锶铁氧体SrFe₁₂O₁₉电子结构及磁性的第一性原理研究[J]. 无机材料学报, 2019, 34(10): 1047-1054.

WANG Zhong, ZHA Xian-Hu, WU Ze, HUANG Qing, DU Shi-Yu. First-principles Study on Electronic and Magnetic Properties of Mn-doped Strontium Ferrite SrFe₁₂O₁₉[J]. Journal of Inorganic Materials, 2019, 34(10): 1047-1054.

图/表 9

图1 锶铁氧体晶胞结构

Fig. 1 The unit cell of SrFe12O19 (a) The green ball denotes the Sr atom, the small grey ball denotes the O atom; (b) The blue, red, purple, magenta, and blue-green balls represent the Fe atoms in 12k, 4f2, 4f1, 2a, and 2b sites, respectively. The spin directions for different Fe3+ are labeled with different colors (black and red)

表1 不同磁构型锶铁氧体的晶格常数、相对能量和净磁矩

Table 1 Lattice parameters, relative total energies and magnetic moments of SrFe12O19 in different magnetic configurations

Spin direction of Fe ions in SrFe₁₂O₁₉					a/nm	c/nm	Energy/(eV?(unit cell)^-1)	Moment/(μ_B?(unit cell)^-1)
2a	2b	4f1	4f2	12k
+	+	+	+	+	0.5730	2.257	0	25.00
-	+	+	+	+	0.5690	2.239	0.5900	48.00
+	-	+	+	+	0.5740	2.266	0.1300	44.00
+	+	-	+	+	0.5770	2.264	0.3200	39.00
+	+	+	-	+	0.5870	2.324	0.4600	59.00
+	+	+	+	-	0.5820	2.300	-1.160	-7.000
-	-	+	-	+	0.5840	2.269	1.040	43.00
-	-	-	+	+	0.5790	2.245	-0.6800	28.00
+	+	-	-	+	0.5860	2.310	-2.820	40.00
					0.5880^a	2.304^a

表2 GGA和GGA+U条件下锶铁氧体的Fe原子磁矩及晶胞总磁矩(μB)

Table 2 Magnetic moments (μB) of Fe atoms and total magnetic moments for SrFe12O19 unit cell from GGA and GGA+U

Atom	Wyckoff site	Coordinates of atoms	Magnetic moment (GGA)	Magnetic moment (GGA+U)
Sr	2d	1/3, 2/3, 3/4	0	0
Fe(1)	2a	0, 0, 0	3.73	4.17
Fe(2)	2b	0, 0, 1/4	3.54	4.05
Fe(3)	4f1	1/3, 2/3, 0.0272	3.43	4.05
Fe(4)	4f2	1/3, 2/3, 0.1909	3.17	4.10
Fe(5)	12k	0.169, 0.338, 0.891	3.71	4.18
Total	–	–	38.5	40.0

图2 基于GGA计算的锶铁氧体的电子能带结构图(a)和总态密度、原子分态密度图(c), 基于GGA+U计算的锶铁氧体的电子能带结构图(b)和总态密度、原子分态密度图(d)

Fig. 2 Electronic band structure (a) and total density of states and atomic projected density (c) of states of SrFe12O19 from GGA, and electronic band structure (b), total density of states and atomic projected density (d) of states of SrFe12O19 from GGA+U

表3 单个Mn原子替代掺杂锶铁氧体不同位置Fe原子的替代能Esub、替代后的晶胞总磁矩mtot和磁矩的改变大小Dmtot

Table 3 Substitution energies of single Mn substituted strontium ferrite with Mn substituted Fe in five different sites, the total magnetic moments of substituted SrFe12-xMnxO19 and their changes relative to the pristine SrFe12O19

Substituted site	E_sub/eV	m_tot/m_B	Dm_tot
2a	-2.24	39.0	-1.00
12k	-2.50	39.0	-1.00
4f1	-1.86	39.0	-1.00
4f2	-2.03	41.0	1.00
2b	-0.34	49.0	9.00

表4 两个Mn原子替换掺杂情况下, SrFe12-xMnxO19(x=1.0)不同构型的取代能Esub, 晶胞磁矩mtot, 以及相对于未掺杂体系的晶胞磁矩变化量Dmtot

Table 4 Substitution energies Esub, total magnetic moments mtot and their changes Dmtot relative to that of the pristine SrFe12O19 for different configurations of SrFe12-xMnxO19(x=1.0) with two Mn atoms substituted

Configurations	E_sub/eV	m_tot/μ_B	Dm_tot
[2a, 2a]	-2.88	38.0	-2.00
[2a, 12k].1	-4.02	38.0	-2.00
[2a, 12k].2	-3.98	38.0	-2.00
[12k, 12k].1	-3.90	38.0	-2.00
[12k, 12k].2	-3.90	38.0	-2.00
[12k, 12k].3	-3.97	38.0	-2.00
[12k, 12k].4	-3.90	38.0	-2.00
[12k, 12k].5	-3.95	38.0	-2.00
[12k, 12k].6	-3.99	38.0	-2.00
[12k, 12k].7	-4.00	38.0	-2.00

表5 锶铁氧体SFO、单个Mn替换12k位置Fe的掺杂模型[12k]、单个Mn替换2a位置Fe的掺杂模型[2a], 以及两个Mn原子掺杂稳定构型[2a,12k].1的四种不同构型中原子磁矩分布

Table 5 Atomic magnetic moments in four different configurations: pristine strontium ferrite SFO, the [12k] configuration that SFO with one 12k Fe atom replaced by Mn, the [2a] configuration that SFO with one 2a Fe atom replaced by Mn, and the [2a,12k].1 structure that the stable configuration of SFO with two Fe atoms replaced by Mn

Site	SFO		[12k]		[2a]		[2a, 12k].1
Site	Atoms	M	Atoms	M	Atoms	M	Atoms	M
2d	2Sr	-0.004	2Sr	-0.003	2Fe	-0.004	2Sr	-0.003
2a	1Fe	4.165	1Fe	4.171	1Mn	3.866	1Mn	3.786
	1Fe	4.165	1Fe	4.164	1Fe	4.164	1Fe	4.164
2b	2Fe	8.108	2Fe	8.135	2Fe	8.132	2Fe	8.137
4f1	4Fe	-16.180	4Fe	-16.181	4Fe	-16.172	4Fe	-16.188
4f2	4Fe	-16.414	4Fe	-16.435	4Fe	-16.414	4Fe	-16.445
12k	1Fe	4.181	1Mn	3.798	1Fe	4.179	1Mn	3.800
	11Fe	45.983	11Fe	45.958	11Fe	45.955	11Fe	45.950
4e	4O	0.716	4O	0.563	4O	0.711	4O	0.517
4f	4O	0.696	4O	0.555	4O	0.673	4O	0.218
6h	6O	0.876	6O	0.870	6O	0.860	6O	0.342
12k	`12O	0.814	12O	0.683	12O	0.311	12O	1.095
12k	12O	1.916	120	1.733	12O	1.821	12O	1.812
Sm		39.02		38.07		38.08		37.09
m_tot		40		39		39		38

表6 未掺杂和Mn掺杂锶铁氧体的晶格常数和体积

Table 6 Lattice constants and volumes of pristine and Mn-doped strontium ferrites

x	a/nm	c/nm	Volume/nm³
0	0.5940	2.319	0.7063
0.5	0.5940	2.319	0.7063
1.0	0.5950	2.320	0.7071

图3 基于GGA+U计算的单个Mn原子掺杂SrFe12-xMnxO19 (x=0.5)的电子能带结构图(a)和总态密度、投影态密度图(c), 基于GGA+U计算的Mn掺杂锶铁氧体(x=1.0)的电子能带结构图(b)和总态密度、投影态密度图(d)

Fig. 3 Electronic band structure (a), total and projected density of states (c) of single Mn substituted SrFe12O19 (x=0.5), and electronic band structure (b), total and projected density of states (d) of Mn substituted SrFe12O19 (x=1.0) based on the GGA+U approach

参考文献 33

[1]	ZHOU X, MA L, LIU T ,et al. Grystal structure and magnetic property of Si₃N₄/FePd/Si₃N₄ thin films.Journal of Inorganic Materials, 2018,33(8):909-915.
[2]	MENG F B, MA X F, ZHANG W ,et al. Structure and magnetic property of Fe and spinel Co₂MnO₄.Journal of Inorganic Materials, 2017,32(6):609-614.
[3]	XIAO L, CHEN Y, LIU Z ,et al. Growth, magnetic and electrical transport properties of La_0.7Sr_0.3MnO₃ thin films on plzst ceramics.Journal of Inorganic Materials, 2017,32(3):326-330.
[4]	ZHANG L, LIU HH, LIU LJ ,et al. Effects of La doping on CaB₆ thin films prepared by DC magnetron sputtering.Journal of Inorganic Materials, 2017,32(5):555-560.
[5]	ZHAO X Y, MAN P W, XIE T ,et al. Crystal growth and characterization of the rare-earth orthoferrite Sm_0.8Tb_0.2FeO₃ single crystal.Journal of Inorganic Materials, 2016,31(9):1004-1008.
[6]	SEEMA V, JOY P A, KHOLLAM Y B ,et al. Synthesis of nanosized MgFe₂O₄ powders by microwave hydrothermal method.Materials Letters, 2004,58(6):1092-1095.
[7]	CHEN D, LIU Y, LI Y, , ,et al.Microstructure. Microstructure and magnetic properties of Al-doped barium ferrite with sodium citrate as chelate agent. Journal of Magnetism and Magnetic Materials, 2013,337- 338:65-69.
[8]	WANG H W, KUNG S C . Crystallization of nanosized Ni-Zn ferrites powders prepared by hydrothermal method. Journal of Magnetism and Magnetic Materials, 2004,270(1/2):230-236.
[9]	ALMESSIERE M A, SLIMANI Y, BAYKAL A ,et al. Structural and magnetic properties of Ce-doped strontium hexaferrite.Ceramics International, 2018,44:9000-9008.
[10]	SEIFERT D ,TÖPFER J, LANGENHORST F ,et al. Synthesis and magnetic properties of La-substituted M-type Sr hexaferrites.Journal of Magnetism and Magnetic Materials, 2009,321(24):4045-4051.
[11]	WANG J F, PONTON C B , GRÖSSINGER R, ,et al. A study of La-substituted strontium hexaferrite by hydrothermal systhesis.Journal of Alloys and Compounds, 2004,369(1/2):170-177.
[12]	WANG J F, PONTON C B, HARRIS I R ,et al. A study of the magnetic properties of hydrothermally synthesisted Sr hexaferrite with Sm substitution.Journal of Magnetism and Magnetic Materials, 2001,234(2):233-240.
[13]	WANG J F, PONTON C B, HARRIS I R ,et al. A study of Pr-substituted strontium hexaferrite by hydrothermal synthesis.Journal of Alloys and Compounds, 2015,403(1/2):104-109.
[14]	WANG J F, PONTON C B, HARRIS I R ,et al. A study of Nd-substituted Sr hexaferrite prepared by hydrothermal synthesis.IEEE Transactions on Magnetic, 2002,38(5):2928-2930.
[15]	ASHIQ M N, IQBAL M J, GUL I H ,et al. Structural, magnetic and dielectric properties of Zr-Cd substituted strontium hexaferrite (SrFe₁₂O₁₉).Journal of Alloys and Compounds, 2009,487(1/2):341-345.
[16]	ASHIQ M N, IQBAL M J , NAJAM-UL-HQ M,et al. Synthesis, magnetic and dielectric properties of Er-Ni doped Sr-hexaferrite nanomaterials for applications in high density recording media and microwave divices.Journal of Magnetism and Magnetic Materials, 2012,324(1):15-19.
[17]	DAVOODI A, HASHEMI B . Magnetic properties of Sn-Mg substituted strontium hexaferrite nanoparticles synthesized via coprecipitation method.Journal of Alloys and Compounds, 2011,509(19):5893-5896.
[18]	CHEN W, WU W W, ZHOU C ,et al. Structural and magnetic properties evolution Co-Nd substituted M-type hexagonal strontium ferrites synthesized by ball-milling-assisted ceramic materials.Journal of Electronic Materials, 2018,47(3):2110-2119.
[19]	EBRAHIMI F, ASHRAFIZADEH F . Tuning the ferromagnetic resonance by doping strontium hexaferrite nanopowders. Journal of Sol-Gel Science and Technology, 2018,85(3):621-628.
[20]	VIVEK D, CHANDANI N ,NANDADASA,et al. Site occupancy and magnetic properties of Al-substituted M-type strontium hexaferrite.Journal of Applied Physics, 2015,17:243904-243912.
[21]	LIYANAGE L S I, KIM S, HONG Y K,et al. Theory of magnetic enhancement in strontium hexaferrite through Zn-Sn pair substitution.Journal of Magnetism and Magnetic Materials, 2013(348):75-81.
[22]	KRESSE G , FURTHMÜLLER J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set.Physics Review B, 1996,54(16):11169-11186.
[23]	KRESSE G ,FURTHMÜLLER J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set.Computation Material Science, 1996,6:15-50.
[24]	PERDEW J P, BURKE K, EMZERHOF M . Generalized gradient approximation made simple. Physics Review Letter, 1996,77:3865-3868.
[25]	BLÖCHL P E . Projector augmented-wave method. Physics Review B, 1994,50:17953-17979.
[26]	KRESSE G, JOUBERT D . From ultrasoft pseudopotentials to the projector augmented-wave method. Physics Review B, 1999,59:1758-1775.
[27]	MONKHORST H, PACK J . Special points for Brillouin-zone interations. Physics Review B, 1976,13:5188-5192.
[28]	LIYANAGE L S I, KIM S, HONG Y K ,et al. Theory of magnetic enhancement in strontium hexaferrite through Zn-Sn pair substitution.Journal of Magnetism and Magnetic Materials, 2013,348:75-81.
[29]	HUANG L H, ZHU Q S, GE W , et al.Oxygen-vacancy formation in LaMO₃( M = Ti, V, Cr, Mn, Fe, Co, Ni) calculated at both GGA and GGA + U levels.Computational Materials Science, 2011,50:1800-1805.
[30]	SAHU B R, BANERJEE S K . Density-functional study of bulk silicon lightly doped with manganese. Physical Review B, 2008,77(15):155203-155209
[31]	GORTER E W . Saturation magnetization of some ferromagnetic oxides with hexagonal crystal structures. Proc. IEEE-Part B: Radio and Electron. Eng, 1957,104:255-260.
[32]	KIMURA K, OHGAKI M, TANAKA K ,et al. Study of the bipyramidal site in magnetoplumbite-like compounds SrM₁₂O₁₉(M=Al, Fe, Ga).Journal Solid State Chemistry, 1990,87:186-194.
[33]	IQBAL M J, FAROOQ S . Impact of Pr-Ni substitution on the electrical and magnetic properties of chemically derived nanosized strontium-barium hexaferrites. Journal of Alloys and Compounds, 2010,505:560-567.

Mn掺杂锶铁氧体SrFe₁₂O₁₉电子结构及磁性的第一性原理研究

First-principles Study on Electronic and Magnetic Properties of Mn-doped Strontium Ferrite SrFe₁₂O₁₉

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