多元纳米稀土六硼化物Nd1–xEuxB6粉末的制备及光吸收研究

潘晓剑; 包黎红; 宁军; 赵凤岐; 朝洛蒙; 刘子忠

doi:10.7498/aps.70.20201288

摘要

在真空环境中采用固相烧结法成功制备出了多元稀土六硼化物Nd_1–_xEu_xB₆纳米粉末. 系统研究了Eu掺杂对纳米NdB₆物相、形貌及光吸收性能的影响规律. 结果表明, 所有合成的纳米粉末物相均为单相的CsCl型晶体结构, 具有立方形貌, 平均晶粒尺度为30 nm. 光吸收实验结果表明, 随着Eu掺杂量的增加, 纳米NdB₆透射光波长从629 nm红移至1000 nm以上, 表现出了透射光波长的可调特性. 此外, NdB₆和EuB₆同步辐射吸收图谱表明, Nd和Eu原子分别以Nd³⁺和Eu²⁺形式存在于纳米NdB₆和EuB₆中, 充分说明了Eu掺杂使NdB₆传导电子数量减少, 从而导致其等离子共振频率能量的降低. 采用第一性原理计算了NdB₆和EuB₆的能带结构、态密度、介电函数以及等离子共振频率能量, 从而定性解释了Eu掺杂使NdB₆透射光波长红移的特性.

关键词:

Abstract

Nanocrystalline rare earth hexaborides Nd_1–_xEu_xB₆ powders are successfully synthesized by the simple solid-state reaction in vacuum condition for the first time. The effect of Eu doping on the crystal structure, grain morphology, microstructure and optical absorption properties of nanocrystalline NdB₆ are investigated by X-ray diffraction, scanning electron microscope (SEM), high resolution transmission electron microscopy (HRTEM) and optical absorption measurements. The results show that all the synthesized samples have a single-phase CsCl-type cubic structure with space group of Pm-3m. The SEM results show that the average grain size of the synthesized Nd_1–_xEu_xB₆ powders is 50 nm. The HRTEM results show that nanocrystalline Nd_1–_xEu_xB₆ has good crystallinity. The results of optical absorption show that the absorption valley of nanocrystalline Nd_1–_xEu_xB₆ is redshifted from 629 nm to higher than 1000 nm with the increase of Eu doping, indicating that the transparency of NdB₆ is tunable. Additionally, the X-ray absorption near-edge structure spectra μ(E) around the Nd and Eu L₃ edges for nanocrystalline NdB₆ and EuB₆ show that total valence of Nd ion is estimated at +3 in nanocrystalline NdB₆ and total valence of Eu ion in nanocrystalline EuB₆ is +2. Therefore, the Eu-doping into NdB₆ effectively reduces the electron conduction number and it leads the plasma resonance frequency energy to decrease. In order to further qualitatively explain the influence of Eu doping on the optical absorption mechanism, the first principle calculations are used to calculate the band structure, density of states, dielectric function and plasma resonance frequency energy. The calculation results show that the electron band of NdB₆ and EuB₆ cross the Fermi energy, indicating that they are typical conductors. In addition, the plasmon resonance frequency can be described in the electron energy loss function. The plasmon resonance frequency energy of NdB₆ and EuB₆ are 1.98 and 1.04 eV, which are corresponding to the absorption valley of 626.26 and 1192.31 nm, respectively. This confirms that the first principle calculation results are in good consistence with the experimental optical absorption valley. Therefore, as an efficient optical absorption material, nanocrystalline Nd_1–_xEu_xB₆ powders can expand the optical application scope of rare earth hexaborides.

Keywords:

作者及机构信息

1.
内蒙古师范大学物理与电子信息学院, 呼和浩特　010022

2.
内蒙古科技大学理学院, 包头　014010

3.
内蒙古师范大学化学与环境科学学院, 呼和浩特　010022

通信作者: 包黎红, baolihong@imnu.edu.cn

基金项目: 国家自然科学基金(批准号: 51662034)、内蒙古自治区自然科学基金联合基金(批准号: 2019LH05001)和内蒙古师范大学研究生科研创新基金(批准号: CXJJS19113)资助的课题

Authors and contacts

1.
College of Physics and Electronic Information, Inner Mongolia Normal University, Hohhot 010022, China

2.
College of science, Inner Mongolia University of Science & Technology, Baotou 014010, China

3.
College of Chemistry and Enviormental Science, Inner Mongolia Normal University, Hohhot 010022, China

Corresponding author: Bao Li-Hong, baolihong@imnu.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 51662034), the Program of Joint Fund of the Natural Science Foundation of Inner Mongolia, China (Grant No. 2019LH05001), and the Graduate Reaserch Innovation Fund of Inner Mongolia Normal University, China (Grant No. CXJJS19113)

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参考文献

[1]	Muz I, Kurban M 2020 J. Alloys Compd. 842 155983 Google Scholar
[2]	Chen X B, Mao S S 2007 Chem. Rev. 107 2891 Google Scholar
[3]	Wang X B, Ji F 2020 J. Nanosci. Nanotechnol. 20 7464 Google Scholar
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施引文献

图 1 稀土六硼化物RB₆ (R = Nd, Eu)的晶体结构, 其中左图为以硼(B)原子为中心的晶体结构, 右图为以稀土(R)原子为中心的晶体结构

Fig. 1. Crystal structure of RB₆ (R = Nd, Eu). Left panel shows the crystal structure centered on the boron atom. Right panel shows the crystal structure centered on rare earth atom.

下载: 全尺寸图片幻灯片

图 2 反应温度为1150 ℃下制备的纳米Nd_1–_xEu_xB₆的XRD图谱

Fig. 2. XRD patterns of the nanocrystalline Nd_1–_xEu_xB₆ prepared at 1150 ℃.

下载: 全尺寸图片幻灯片

图 3 纳米晶Nd_1–_xEu_xB₆(x = 0, 0.2, 0.4, 0.6, 0.8)的SEM照片

Fig. 3. SEM images of nanocrystalline Nd_1–_xEu_xB₆ (x = 0, 0.2, 0.4, 0.6, 0.8).

下载: 全尺寸图片幻灯片

图 4 (a) 纳米Nd_0.4Eu_0.6B₆的TEM照片; (b) HRTEM照片和快速傅里叶变换照片; (c) 纳米Nd_0.4Eu_0.6B₆的HAADF照片; (d)−(f) Nd_0.4Eu_0.6B₆中的Nd, Eu和B元素分布

Fig. 4. (a) TEM image of nanocrystalline Nd_0.4Eu_0.6B₆; (b) HRTEM image and fast Fourier transform pattern; (c) HAADF image of Nd_0.4Eu_0.6B₆; (d)−(f) elemental distribution of Nd, Eu and B for nanocrystalline Nd_0.4Eu_0.6B₆.

下载: 全尺寸图片幻灯片

图 5 纳米Nd_1–_xEu_xB₆粉末光吸收曲线

Fig. 5. Optical absorption spectrum of nanocrystalline Nd_1–_xEu_xB₆ powder.

下载: 全尺寸图片幻灯片

图 6 第一性原理计算的能带结构图　(a) NdB₆; (b) EuB₆

Fig. 6. First-principle calculation results of band structure: (a) NdB₆; (b) EuB₆.

下载: 全尺寸图片幻灯片

图 7 第一性原理计算的总态密度和部分态密度曲线　(a) NdB₆; (b) EuB₆

Fig. 7. First-principle calculation results of total density of states (TDOS) and partial density of states (PDOS) curves: (a) NdB₆; (b) EuB₆.

下载: 全尺寸图片幻灯片

图 8 介电函数的实部ε₁和虚部ε₂　(a) NdB₆; (b) EuB₆

Fig. 8. Real part ε₁ and imaginary part ε₂ of the dielectric function: (a) NdB₆; (b) EuB₆.

下载: 全尺寸图片幻灯片

图 9 能量损失函数曲线　(a) NdB₆; (b) EuB₆

Fig. 9. Energy loss function curves: (a) NdB₆; (b) EuB₆.

下载: 全尺寸图片幻灯片

图 10 纳米NdB₆和EuB₆同步辐射吸收图谱　(a) Nd-L₃和Eu-L₃边总X射线吸收光谱; (b) Nd-L₃边局部放大; (c) Eu-L₃边局部放大

Fig. 10. Synchrotron radiation absorption spectrum of nanocrystalline NdB₆ and EuB₆: (a) total X-ray absorption spectra of Nd-L₃ and Eu-L₃; (b) partial enlargement of Nd-L₃; (c) partial enlargement of Eu-L₃.

下载: 全尺寸图片幻灯片

map

[1]	Muz I, Kurban M 2020 J. Alloys Compd. 842 155983 Google Scholar
[2]	Chen X B, Mao S S 2007 Chem. Rev. 107 2891 Google Scholar
[3]	Wang X B, Ji F 2020 J. Nanosci. Nanotechnol. 20 7464 Google Scholar
[4]	Xiao Q F, Zheng X P, Bu W B, Ge W Q, Zhang S J, Chen F, Xing H Y, Ren Q G, Fan W P, Zhao K L, Hua Y Q, Shi J L 2013 J. Am. Chem. Soc. 135 13041 Google Scholar
[5]	Lv R C, Yang P P, He F, Gai S, Li C X, Dai Y L, Yang G X, Lin J 2015 ACS Nano 9 1630
[6]	Yuan Y F, Zhang L, Hu L J, Wang W, Min G H 2011 J. Solid State Chem. 184 3364 Google Scholar
[7]	Takeda H, Kuno H, Adachi K 2008 J. Am. Ceram. Soc. 91 2897 Google Scholar
[8]	Schelm S, Smith G B 2003 Appl. Phys. Lett. 82 4346 Google Scholar
[9]	Lai B H, Chen D H 2013 Acta Biomater. 9 7556 Google Scholar
[10]	Chen M C, Lin Z W, Ling M H 2016 ACS Nano 10 93 Google Scholar
[11]	Wang Y, Fang C, Li X, Li Z P, Liu B H 2019 J. Alloys Compd. 803 757 Google Scholar
[12]	Xiao L H, Su Y C, Zhou X Z, Chen H Y, Tan J, Hu T, Yan J, Peng P 2012 Appl. Phys. Lett. 101 041913 Google Scholar
[13]	肖立华, 伏云昌, 苏玉长, 张鹏飞, 彭平 2011 原子与分子 28 0176 Xiao L H, Fu Y C, Su Y C, Zhang P F, Peng P 2011 J. At. Mol. Phys. 28 0176
[14]	Xiao L H, Su Y C, Chen H Y, Jiang M, Liu S N, Hu Z X, Liu R F, Peng P, Mu Y L, Zhu D Y 2011 AIP Adv. 1 022140 Google Scholar
[15]	Bao L H, Qi X P, Tana, Chao L M, Tegus O 2016 CrystEngComm 18 1223 Google Scholar
[16]	Bao L H, Qi X P, Tana, Chao L M, Tegus O 2016 Phys. Chem. Chem. Phys. 18 19165 Google Scholar
[17]	Bao L H, Chao L M, Li Y J, Ming M, Yibole B, Tegus O 2015 J. Alloys Compd. 651 19 Google Scholar
[18]	Bao L H, Chao L M, Wei W, Tegus O 2015 Mater. Lett. 139 187 Google Scholar
[19]	Bao L H, Wurentuya B, Wei W, Li Y J, Tegus O 2014 J. Alloys Compd. 617 235 Google Scholar
[20]	Zhang X J, Tsai Y T, Wu S M, Lin Y C, Lee J F, Sheu H S, Cheng B M, Liu R S 2016 ACS Appl. Mater. Interfaces 8 19612 Google Scholar
[21]	Kerisit S N, Prange M P 2020 Chem. Geol. 534 119460 Google Scholar
[22]	Qi X P, Bao L H, Chao L M, Tegus O 2018 Physica B 530 312 Google Scholar
[23]	Kimura S, Nanba T, Tomikawa M, Kunii S, Kasuya T 1992 Phys. Rev. B 46 12196 Google Scholar
[24]	Choi Y G, Lee K A, Lee K S 2007 Met. Mater. Int. 13 269 Google Scholar
[25]	Hernandez R E R, Marcos F R, Serrano A, Salas E, Hussainova I, Fernandez J F 2019 Nanomaterials 9 1473 Google Scholar

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多元纳米稀土六硼化物Nd_1–_xEu_xB₆粉末的制备及光吸收研究