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最近研究发现, AB(N,O)3型钙钛矿氧氮化物具有优异的介电、铁电、光催化等性能, 在光电子、能源存储和通信等领域展现出广阔的应用前景. 但是, 目前该类型材料的制备工艺耗时较长且产物纯度较低. 本文以氧化物为前驱体、以氨基钠为氮源, 利用六面顶压机设备所提供的高温高压环境成功制备了高纯度的钙钛矿型氧氮化物CeTaN2O块体材料, 并将制备时间缩短至1 h, 实现了快速合成. 并对其晶体结构以及物理性质进行了系统的研究. X射线粉末衍射实验和Rietveld精修结果表明, 所制备的样品属于正交晶系, 空间群为Pnma. X射线吸收谱测试确定了样品的电荷组态以及阴离子组合为Ce3+Ta5+N2O. 磁性和比热测试表明, 样品属于反铁磁物质, 磁相变温度低于2 K. 电学输运性能测试表明, 样品的电阻率呈现出典型的半导体行为, 且符合三维变程跳跃模型.Recently, it has been discovered that the AB(N,O)3-type perovskite oxynitrides exhibit excellent dielectric, ferroelectric, and photocatalytic properties, promising for applications in the fields of optoelectronics, energy storage, and communication. Due to the differences in charge, ionic radius, and covalent bonding between N3– ion and O2– ion, the N substitution for O enhances the B(N,O)6 octahedron tilting, giving rise to exotic properties and functionalities. However, the current fabrication process for this type of material is rather time-consuming, leading to products with an appreciable quantity of impurities. In this study, using oxide precursors and sodium amide as the nitrogen source, high-purity perovskite-type oxynitride CeTaN2O bulk materials are successfully synthesized under high-temperature and high-pressure conditions provided by a cubic-anvil press. The synthesis time decreases to 1 h, achieving rapid production. The lattice structure and physical properties of the obtained samples are comprehensively investigated. X-ray powder diffraction experiments and subsequent Rietveld refinement indicate that the title material shows an orthorhombic crystal structure with the space group of Pnma. The X-ray absorption spectra confirm the charge configuration and the anion composition as Ce3+Ta5+N2O. Magnetization and specific heat measurements reveal that the exchange interactions are mainly antiferromagnetic, with a potential magnetic transition below 2 K. The electrical transport data demonstrate typical semiconductor behaviors, which can be further explained by a three-dimensional variable-range hopping model. Our study paves the way for putting this exotic perovskite oxynitride into practical applications.
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Keywords:
- high-pressure synthesis /
- perovskite-type nitride /
- antiferromagnetic /
- semiconductor
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图 1 ABO3 (a)与AB(N, O)3 (b)钙钛矿的晶体结构示意图
Fig. 1. Schematic crystal structures for ABO3 (a) and AB(N, O)3 perovskites (b).
图 2 室温下CeTaN2O的XRD图谱和结构精修结果, 插图给出了晶体结构示意图
Fig. 2. XRD pattern and structure refinement results of CeTaN2O obtained at room temperature. The inset shows a schematic diagram of the crystal structure.
图 3 (a) Ce-M4,5; (b) Ta-L3的XAS. 图中给出了相关的参考样品作为对比
Fig. 3. XAS at (a) Ce-M4,5 edges and (b) Ta-L3 edges. The XAS of related references are also shown for comparison.
图 4 (a) 0.1 T磁场下磁化率和磁化率倒数随温度的变化关系, 其中蓝线代表100 K以上的居里-外斯拟合结果; (b) 不同温度下磁化强度随磁场的变化关系
Fig. 4. (a) Temperature dependence of magnetic susceptibility and the inverse susceptibility at 0.1 T. The blue line shows the Curie-Weiss fitting above 100 K; (b) field dependent magnetization measured at different temperatures.
图 5 CeTaN2O比热随温度的变化曲线, 插图是各个磁场下的低温比热
Fig. 5. Plot of specific heat vs. temperature. The inset shows the specific heat under various magnetic fields.
图 6 CeTaN2O电阻率随温度的变化曲线. 插图是将100—300 K的电阻率用三维变程跳跃模型拟合得到的结果
Fig. 6. Temperature-dependent resistivity of CeTaN2O. The inset shows the fitting result using the 3D variable-range hopping model.
表 1 CeTaN2O的精修结构参数
Table 1. Refined structure parameters of CeTaN2O.
Space group Pnma a/Å 5.69575(9) Rwp/% 3.28 b/Å 8.03326(8) Rp/% 2.30 c/Å 5.70427(8) χ2 2.71 Atomic position(s) atom site x y z occ Uiso/Å2 Ce 4c 0.01792(8) 0.25 0.99101(2) 1 0.0086(5) Ta 4b 0.5 0 0 1 0.0055(9) N/O 4c 0.49062(2) 0.25 0.14377(9) 0.67/0.33 0.01 N/O 8d 0.26950(2) 0.03833(9) 0.76871(6) 0.67/0.33 0.01 
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[1] Tobías G, Oró-Solé J, Beltrán-Porter D, Fuertes A 2001 Inorg. Chem. 40 6867
Google Scholar
[2] Marchand R, Pors F, Laurent Y, Regreny O, Lostec J, Haussonne J M 1986 J. Phys. Colloques 47 C1
Google Scholar
[3] Kim Y I, Woodward P M, Baba-Kishi K Z, Tai C W 2004 Chem. Mater. 16 1267
Google Scholar
[4] Jorge A B, Oró-Solé J, Bea A M, Mufti N, Palstra T T M, Rodgers J A, Attfield J P, Fuertes A 2008 J. Am. Chem. Soc. 130 12572
Google Scholar
[5] Yang M, Oró-Solé J, Kusmartseva A, Fuertes A, Attfield J P 2010 J. Am. Chem. Soc. 132 4822
Google Scholar
[6] Maeda K, Domen K 2007 J. Phys. Chem. C 111 7851
Google Scholar
[7] Li Y Q, Delsing A C A, de With G, Hintzen H T 2005 Chem. Mater. 17 3242
Google Scholar
[8] Shannon R D 1976 Acta Crystallogr. Sect. A 32 751
Google Scholar
[9] 叶施亚, 李端, 李俊生, 曾良, 曹峰 2021 人工晶体学报 50 187
Ye S Y, Li D, Li J S, Zeng L, F C 2021 J. Synth. Cryst. 50 187
[10] Porter S H, Huang Z, Woodward P M 2014 Cryst. Growth Des. 14 117
Google Scholar
[11] Porter S H, Huang Z, Cheng Z, Avdeev M, Chen Z, Dou S, Woodward P M 2015 J. Solid State Chem. 226 279
Google Scholar
[12] Page K, Stoltzfus M W, Kim Y I, Proffen T, Woodward P M, Cheetham A K, Seshadri R 2007 Chem. Mater. 19 4037
Google Scholar
[13] Badding J V 1998 Annu. Rev. Mater. Sci. 28 631
Google Scholar
[14] Brazhkin V V 2007 High Pressure Res. 27 333
Google Scholar
[15] Rietveld H M 1969 J. Appl. Crystallogr. 2 65
Google Scholar
[16] Roth R S, Negas T, Parker H S, Minor D B, Jones C 1977 Mater. Res. Bull. 12 1173
Google Scholar
[17] Santoro A, Marezio M, Roth R S, Minor D 1980 J. Solid State Chem. 35 167
Google Scholar
[18] 殷云宇, 王潇, 邓宏芟, 周龙, 戴建洪, 龙有文 2017 物理学报 66 030201
Google Scholar
Yin Y Y, Wang X, Deng H S, Zhou L, Dai J H, Long Y W 2017 Acta Phys. Sin. 66 030201
Google Scholar
[19] Deminami S, Kawamura Y, Chen Y Q, Kanazawa M, Hayashi J, Kuzuya T, Takeda K, Matsuda M, Sekine C 2017 J. Phys. Conf. Ser. 950 042032
Google Scholar
[20] Sekine C, Sai U, Hayashi J, Kawamura Y, Bauer E 2017 J. Phys. Conf. Ser. 950 042028
Google Scholar
[21] Kabeya N, Takahara S, Satoh N, Nakamura S, Katoh K, Ochiai A 2018 Phys. Rev. B 98 035131
Google Scholar
[22] Nakano T, Onuma S, Takeda N, Uhlířová K, Prokleška J, Sechovský V, Gouchi J, Uwatoko Y 2019 Phys. Rev. B 100 035107
Google Scholar
[23] Matin M, Kulkarni R, Thamizhavel A, Dhar S K, Provino A, Manfrinetti P 2017 J. Phys Condens. Matter 29 145601
Google Scholar
[24] Ajeesh M O, Kushwaha S K, Thomas S M, Thompson J D, Chan M K, Harrison N, Tomczak J M, Rosa P F S 2023 Phys. Rev. B 108 245125
Google Scholar
[25] Ravot D, Burlet P, Rossat-Mignod J, Tholence J L 1980 J. Phys. 41 1117
Google Scholar
[26] Mott N F 1969 Philos. Mag. 19 835
Google Scholar
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