氮化铁薄膜晶相合成热分析及其磁性

卢启海; 唐晓莉; 宋玉哲; 左显维; 韩根亮; 闫鹏勋; 刘维民

doi:10.7498/aps.68.20182195

摘要

研究Fe-N体系晶相转变(相变)规律对于高效合成高自旋极化率的γ'-Fe₄N薄膜材料非常重要. 利用同步热分析(TG-DSC)研究了氮化铁薄膜的相变规律. TG-DSC的结果显示, 在10 ℃/min的升温速率下, γ''-FeN薄膜在常温到800 ℃之间共有5次相变, 分别为I, γ''-FeN→ξ-Fe₂N; II, ξ-Fe₂N→ε-Fe₃N; III, ε-Fe₃N→γ'-Fe₄N; IV, γ'-Fe₄N→γ-Fe; 以及V, γ-Fe→α-Fe. 利用真空退火技术有效调控了氮化铁薄膜的晶相. X-射线衍射测试结果显示, 直接在纯氮气中溅射得到的氮化铁薄膜是单相的γ''-FeN, 经350, 380和430 ℃退火可分别获得单相的ξ-Fe₂N, ε-Fe₃N和γ'-Fe₄N. 研究了氮化铁薄膜的磁学性能. 振动样品磁强计测试结果显示, γ'-Fe₄N薄膜在面内/面外表现出明显的磁各向异性, 属于典型的磁形状各向异性.

关键词:

Abstract

The phase transition law of Fe-N system is very important for efficiently synthesizing single-phase γ'-Fe₄N thin films. The γ"-FeN thin films are deposited on silicon wafers via DC reactive magnetron sputtering; some of them are stripped from the silicon wafers and measured by using the synchronous thermal analysis (TG-DSC) for studying the phase transition law of Fe-N system. The results of TG-DSC show that at a heating rate of 10 ℃/min, the Fe-N system has five phase transitions in a temperature range between room temperature (RT) and 800 ℃, i.e. I (330−415 ℃): γ''-FeN→ξ-Fe₂N with an endothermic value of 133.8 J/g; II (415−490 ℃): ξ-Fe₂N→ε-Fe₃N with no obvious latent heat of phase change; III (510−562 ℃): ε-Fe₃N→γ'-Fe₄N with an exotherm value of 29.3 J/g; IV (590−636 ℃): γ'-Fe₄N→γ-Fe with an exotherm value of 42.6 J/g; V (636−690 ℃): γ-Fe→α-Fe with an endothermic value of 14.4 J/g. According to the phase transition law of Fe-N system, the crystal phase of iron nitride thin film is effectively regulated by vacuum annealing. The x-ray diffraction pattern (XRD) results show that the iron nitride thin film obtained by direct-sputtering in pure N₂ is a single-phase γ"-FeN film, and it becomes a single-phase ξ-Fe₂N film after being annealed at 350 ℃ for 2 h, a single-phase ε-Fe₃N film after being annealed at 380 ℃ for 2 h, and a single-phase γ'-Fe₄N film after being annealed at 430 ℃ for 7 h. The annealing temperature for the phase transition of Fe-N thin film is generally lower than that predicted by the TG-DSC experimental results, because it is affected by the annealing time too, that is, prolonging the annealing time at a lower temperature is also effective for regulating the crystal phase of Fe-N thin film. The magnetic properties of the Fe-N thin film are also studied via vibrating sample magnetometer (VSM) at room temperature. The γ'-Fe₄N polycrystalline thin film shows an easy-magnetized hysteresis loop for the isotropic in-plane one, but a hard-magnetized hysteresis loop with a large demagnetizing field for the out-of-plane one, which belongs to the typical magnetic shape anisotropy. However, their saturation magnetizations are really the same (about 950 emu/cm³) both in the plane and out of the plane.

Keywords:

作者及机构信息

1.
甘肃省科学院传感技术研究所, 甘肃省传感器与传感技术重点实验室, 兰州　730000

2.
电子科技大学, 电子薄膜与集成器件国家重点实验室, 成都　610054

3.
甘肃省科学院纳米应用技术研究室, 兰州　730000

4.
中国科学院兰州化学物理研究所, 兰州　730000

通信作者: 唐晓莉, tangtang122@uestc.edu.cn

基金项目: 电子薄膜与集成器件国家重点实验室开放课题(批准号: KFJJ201703)、国家自然科学基金(批准号: 51772047)、国家自然科学基金地区科学基金(批准号: 51761001, 51665003, 21864003)、甘肃省自然科学基金(批准号: 17JR5RA180)、兰州市人才创新创业项目(批准号: 2016-RC-80)和2018年度“西部青年学者”项目资助的课题.

Authors and contacts

1.
Key Laboratory of Sensor and Sensing Technology of Gansu Province, Institute of Sensor Technology, Gansu Academy of Sciences, Lanzhou 730000, China

2.
State Key Laboratory of Electronic Thin Films and Integrated Devices, University of Electronic Science and Technology of China, Chengdu 610054, China

3.
Institute of Nano-materials Application Technology, Gansu Academy of Sciences, Lanzhou 730000, China

4.
Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China

Corresponding author: Tang Xiao-Li, tangtang122@uestc.edu.cn

Funds: Project supported by the Open Foundation of State Key Laboratory of Electronic Thin Films and Integrated Devices, China (Grant No. KFJJ201703), the National Natural Science Foundation of China (Grant No. 51772047), the Fund for Less Developed Regions of the National Natural Science Foundation of China (Grant Nos. 51761001, 51665003, 21864003), the Natural Science Foundation of Gansu Province, China (Grant No. 17JR5RA180), the Lanzhou Talent Innovation and Entrepreneurship Project, China (Grant No. 2016-RC-80), and the 2018 "Western Young Scholars" Project.

文章全文 : translate this paragraph

参考文献

[1]	de Groot R A, Mueller F M, van Engen P G, et al. 1983 Phys. Rev. Lett. 50 2024 Google Scholar
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施引文献

图 1 Fe-N体系相图^[24]

Fig. 1. Phase diagram of Fe-N system^[24].

下载: 全尺寸图片幻灯片

图 2 溅射得到的氮化铁薄膜的AFM图谱

Fig. 2. AFM spectrum of the iron nitride film obtained by sputtering.

下载: 全尺寸图片幻灯片

图 3 不同温度退火2 h前后的氮化铁薄膜的XRD图谱

Fig. 3. XRD patterns of iron nitride films before and after annealing at different temperatures for 2 hours.

下载: 全尺寸图片幻灯片

图 4 430 ℃退火不同时间的氮化铁薄膜的XRD图谱^[29]

Fig. 4. XRD pattern of iron nitride films with different annealing time at 430 ℃^[29].

下载: 全尺寸图片幻灯片

图 5 氮化铁薄膜的TG-DSC曲线(虚线为DTG, 是TG的一阶导数)

Fig. 5. TG-DSC curves of iron nitride film (dotted line is DTG, which is the first derivative of TG).

下载: 全尺寸图片幻灯片

图 6 氮化铁薄膜的面内VSM图谱

Fig. 6. In-plane VSM pattern of iron nitride films.

下载: 全尺寸图片幻灯片

图 7 γ'-Fe₄N薄膜的面内和面外VSM图谱

Fig. 7. In-plane & out-of-plane VSM pattern of the γ'-Fe₄N film

下载: 全尺寸图片幻灯片

表 1 TG-DSC曲线关键节点处Fe-N的化学组分、主要晶相和晶型

Table 1. Chemical composition, main crystal phase, and crystal form of the Fe-N at key nodes of the TG-DSC curve.

温度/℃	化学组分	主要晶相	晶型
330	FeN_1.1	γ''-FeN	立方
415	Fe₂N_1.3	ξ-Fe₂N	六角
490	Fe₃N_1.4	ε-Fe₃N	六角
510	Fe₃N_1.3	ε-Fe₃N	六角
562	Fe₄N	γ'-Fe₄N	立方 (Fe构成面心立方, N位于体心)
590	Fe₄N_0.7	γ'-Fe₄N	立方
636	Fe₄N_0.37	γ-Fe	面心立方
690	Fe	α-Fe	体心立方

下载: 导出CSV

[1]	de Groot R A, Mueller F M, van Engen P G, et al. 1983 Phys. Rev. Lett. 50 2024 Google Scholar
[2]	任尚坤, 张凤鸣, 都有为 2004 物理学进展 24 381 Google Scholar Ren S K, Zhang F M, Du Y W 2004 Prog. Phys. 24 381 Google Scholar
[3]	Strijkers G J, Ji Y, Yang F Y, et al. 2001 Phys. Rev. B 63 104510 Google Scholar
[4]	Vahidi M, Gifford J A, Zhang S K, et al. 2014 APL Mater. 2 046108 Google Scholar
[5]	Li S, Takahashi Y K, Sakuraba Y, et al. 2016 Appl. Phys. Lett. 108 122404 Google Scholar
[6]	Bosu S, Sakuraba Y, Sasaki T T, et al. 2016 Scripta Mater. 110 70 Google Scholar
[7]	Ramsteiner M, Brandt O, Flissikowski T, et al. 2008 Phys. Rev. B 78 121303 Google Scholar
[8]	Bruski P, Manzke Y, Farshchi R, et al. 2013 Appl. Phys. Lett. 103 052406 Google Scholar
[9]	张炜, 千正男, 隋郁, 等 2005 物理学报 54 4879 Google Scholar Zhang W, Qian Z N, Sui Y, et al. 2005 Acta Phys. Sin. 54 4879 Google Scholar
[10]	王本阳, 千正男, 隋郁, 等 2005 物理学报 54 3386 Google Scholar Wang B Y, Qian Z N, Sui Y, et al. 2005 Acta Phys. Sin. 54 3386 Google Scholar
[11]	Ji Y, Strijkers G J, Yang F Y, et al. 2001 Phys. Rev. Lett. 86 5585 Google Scholar
[12]	Ding Y, Yuan C, Wang Z, et al. 2014 Appl. Phys. Lett. 105 092401 Google Scholar
[13]	Wada E, Watanabe K, Shirahata Y, et al. 2010 Appl. Phys. Lett. 96 102510 Google Scholar
[14]	唐晓莉, 张怀武, 苏桦, 等 2006 无机材料学报 21 741 Google Scholar Tang X L, Zhang H W, Su Y, et al. 2006 J. Inorg. Mater. 21 741 Google Scholar
[15]	Wang L L, Zheng W T, Gong J, et al. 2009 J. Alloy. Compd. 467 1 Google Scholar
[16]	Mi W B, Guob Z B, Fenga X P, et al. 2013 Acta Mater. 61 6387 Google Scholar
[17]	Kokado S, Fujima N, Harigaya K, et al. 2006 Phys. Rev. B 73 172410 Google Scholar
[18]	Wang X, Zheng W T, Tian H W, et al. 2003 Appl. Surf. Sci. 220 30 Google Scholar
[19]	Wang L L, Wang X, Ma N, et al. 2006 Surf. Coat. Tech. 201 786 Google Scholar
[20]	Wang L L, Wang X, Zheng W T, et al. 2006 Mater. Chem. Phys. 100 304 Google Scholar
[21]	Navío C, Alvarez J, Capitan M J, et al. 2009 Appl. Phys. Lett. 94 263112 Google Scholar
[22]	Zhang Q, Yang S A, Mi W, et al. 2016 Adv. Mater. 28 959 Google Scholar
[23]	Mi W B, Feng X P, Duan X F, et al. 2012 Thin Solid Films 520 7035 Google Scholar
[24]	Zhang Y, Mi W, Wang X, et al. 2015 Phys. Chem. Chem. Phys. 17 15435 Google Scholar
[25]	Mi W B, Feng X P, Bai H L 2011 J. Magn. Magn. Mater. 323 1909 Google Scholar
[26]	米文博, 王晓姹 2015 高自旋极化磁性材料(天津: 天津大学出版社) 第124页 Mi W B, Wang X C 2015 High Spin Polarized Magnetic Materials (Tianjin: Tianjin University Press) p124 (in Chinese)
[27]	Widenmeyer M, Niewa R, Hansen T C, et al. 2013 Z. Anorg. Allg. Chem. 639 285 Google Scholar
[28]	Widenmeyer M, Hansen T C, Meissner E, et al. 2014 Z. Anorg. Allg. Chem. 640 1265 Google Scholar
[29]	Lu Q, Xie M, Han G, et al. 2019 J. Magn. Magn. Mater. 474 76 Google Scholar
[30]	Mohn P, Matar S F 1999 J. Magn. Magn. Mater. 191 234 Google Scholar

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