第一原理研究LuPO4中氧空位的性质

doi:10.15541/jim20180431

摘要/Abstract

摘要：

磷酸结构的晶体在掺杂二价阳离子后容易形成产生焦磷酸结构(P₂O₇) ^4-, 这种含有焦磷酸结构的氧化物材料十分适合做质子导体、燃料电池、气体传感器以及陶瓷膜等。本文利用第一性原理研究了LuPO₄晶体中氧空位的结构性质, 结果显示当氧空位带二价正电时, 会引发氧空位周围原子奇特的畸变, 形成焦磷酸结构。为了解释这种结构畸变的机理, 本文利用过渡态搜索计算了结构变化过程中势能面的变化情况, 正一价氧空位形成焦磷酸结构需要越过2.4 eV的势垒, 而正二价氧空位形成焦磷酸结构则不需要越过任何势垒, 因此很容易形成焦磷酸结构。最后给出氧空位不同带电态的晶格结构、电子态密度以及电荷密度分布等基本物理性质, 氧空位处于正二价态结构下, 氧空位附近的P原子与O原子成键, 又由于O原子有较强的电负性, P的s轨道电子向O的p轨道转移。P的s、p轨道在禁带中出现了与总态密度对应的缺陷能级, 结果表明带正二价氧空位的晶体性质发生了明显变化。

关键词: 第一性原理, LuPO₄, 氧空位, 过渡态搜索

Abstract:

Phosphoric acid crystal doped with bivalent cation is easy to form pyrophosphate structure (P₂O₇) ^4-. This kind of oxide material containing pyrophosphate structure is very suitable for proton conductor, fuel cell, gas sensor, and ceramic film, etc. In this research we applied first principles to study the structural behaviour of oxygen vacancy in LuPO₄ crystal. The results showed that oxygen vacancies with two positive charges distort structure largely and form pyrophosphate structure. In order to verify the feasibility of this structure transition, the nudged elastic band method is used to find the highest saddle point of potential energy. The calculated results show that transition state energies of oxygen vacancy with +1 and +2 charge forming pyrophosphate structure are about 2.4 and 0 eV, respectively. So pyrophosphate structure easily forms for oxygen vacancy with +2 charge. Finally, the lattice structure, density of states and charge density distribution are obtained. P atom and O atom around the oxygen vacancy with +2 charge can form chemical bond. The electron on the P s will shift to O p orbit for oxygen with strong electronegative, which introduces the defect level in forbidden band. It is indicated that the property of the crystal changes drastically for the existence of the oxygen vacancy with two positive charges.

Key words: first principle, LuPO₄, oxygen vacancy, nudged elastic band method

中图分类号:

李金, 刘廷禹, 姚舒安, 付明雪, 鲁晓晓. 第一原理研究LuPO₄中氧空位的性质[J]. 无机材料学报, 2019, 34(8): 879-884.

LI Jin, LIU Ting-Yu, YAO Shu-An, FU Ming-Xue, LU Xiao-Xiao. First Principles Study on the Property of O Vacancy in LuPO₄ Crystal[J]. Journal of Inorganic Materials, 2019, 34(8): 879-884.

图/表 10

图1 四方锆石结构的LuPO4超原胞

Fig. 1 Tetragonal zircon structure of LuPO4 supercell

图2 含Vo的LuPO4晶格在不同价态下的结构

Fig. 2 Structure of an O vacancy in LuPO4 which in different charge states

表1 完整超原胞和含不同价态下氧空位晶体的结构参数(nm)

Table 1 Calculated structural parameters for the neutral and charged oxygen vacancy (nm)

Bond	Perfect	0(Neutral state)	+1(Charged state)	+2(Charged state)
P(1)-O(1)	0.1552	0.1557	0.1559	0.1525
P(1)-O(2)	0.1552	0.1547	0.1546	0.1518
P(1)-O(3)	0.1552	0.1557	0.1559	0.1525
P(1)-O(4)	0.1552	0.1547	0.1548	0.1625
P(1)-P(2)	0.3740	0.3948	0.3737	0.2907
P(2)-O(5)	0.1552	0.1618	0.1552	0.1520
P(2)-O(6)	0.1552	0.1606	0.1539	0.1518
P(2)-O(7)	0.1552	0.1606	0.1539	0.1518
P(2)-O(4)	0.3322	0.3497	0.3244	0.1684

图3 过渡态搜索计算得到的能量路径(Vo处于正二价态)

Fig. 3 Energy path way calculated with nudged elastic band method for oxygen vacancy with two positive charges

图4 过渡态搜索计算的最低能量路径(Vo处于正一价态), 峰值大约2.4 eV

Fig. 4 Energy path way calculated with nudged elastic band method for oxygen vacancy with one positive charges. Peak located at ~2.4 eV

图5 完整结构以及含缺陷晶格的电荷密度分布图

Fig. 5 Charge density distribution for pure and defective crystals

图6 不同结构下总态密度图

Fig. 6 Tolal density of states under different structures

图7 不同结构下O(4)原子p轨道的分波态密度图

Fig. 7 Partial density of states for p orbital of the O(4) atom under different structures

图8 不同结构下P(2)原子s轨道的分波态密度图

Fig. 8 Partial density of states for s orbital of the s(2) atom under different structures

图9 不同结构下P(2)原子p轨道的分波态密度图

Fig. 9 Partial density of states for p orbital of the P(2) atom under different structures

参考文献 24

[1]	PHADKEP S, NINO J C, ISLAM M S . Structural and defect properties of the LaPO₄ and LaP₅O₁₄-based proton conductors. Journal of Materials Chemistry, 2012,22(48):25388-25394. DOI URL
[2]	SOLOMON J, ADELSTEIN N, ASTA M , et al. Charge-compensating pyrophosphate defect structures in Sr-doped LaPO₄. ECS Transactions, 2012,45(1):117-120.
[3]	AMEZAWZ K, MAEKAWA H, TOMII Y , et al. Protonic conduction and defect structures in Sr-doped LaPO₄. Solid State Ionics, 2001,145(1-4):233-240.
[4]	KITAMURA N, AMEZAWA K, TOMII Y , et al. High temperature protonic conduction in Sr-doped NdPO₄. Journal of the Japan Society of Powder and Powder Metallurgy, 2002,49(10):856-860.
[5]	KITAMURA N, AMEZAWA K, TOMII Y , et al. Protonic conduction in rare earth orthophosphates with the monazite structure. Solid State Ionics, 2003,162:161-165.
[6]	AMEZAWA K, TOMII Y, YAMAMOTO N . High temperature protonic conduction in Ca-doped YPO₄. Solid State Ionics, 2003,162:175-180.
[7]	RAPAPORT A, DAVID V, BASS M , et al. Optical spectroscopy of erbium-doped lutetium orthophosphate. Journal of Luminescence, 1999,85(1/2/3):155-161.
[8]	SUN C, LI X, WANG H , et al. Crystallization-dependent luminescence properties of Ce: LuPO₄. Inorganic Chemistry, 2016,55(6):2969-2976.
[9]	LEMPICKI A, BERMAN E, WOJTOWICZ A J , et al. Cerium- doped orthophosphates: new promising scintillators. IEEE Transactions on Nuclear Science, 1993,40(4):384-387.
[10]	MAKHOV V N, KIRIKOVA N Y, KIRM M , et al. Luminescence properties of YPO₄: Nd³⁺: a promising VUV scintillator material. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment , 2002,486(1/2):437-442.
[11]	VISTOVSKYY V, MALYI T, VAS’KIV A , et al. Luminescent properties of LuPO₄-Pr and LuPO₄-Eu nanoparticles. Journal of Luminescence, 2016,179:527-532.
[12]	LI WEI, SUN YI-YANG, LI LIN-QIN . Control of charge recombination in perovskites by oxidation state of halide vacancy. Journal of the American Chemical Society, 2018,140(46):15753-15763. DOI URL
[13]	LI JING, LIU TINGYU, FU MINGYUE , et al. Optical properties simulating calculation of the F or F + center in LuPO₄ crystal. Acta Phtonica Sinca, 2018,47(7):1-7.
[14]	NIPKO J C, LOONG C K, LOEWENHAUPT M , et al. Lattice dynamics of xenotime: the phonon dispersion relations and density of states of LuPO₄. Physical Review B, 1997,56(18):11584-11592.
[15]	NIPKO J C, LOONG C K, LOEWENHAUPT M , et al. Lattice Dynamics of LuPO₄. Journal of Alloys and Compounds, 1997,250(1/2):573-576.
[16]	KRESSE G, FURTHMULLER J . Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Physical Review B, 1996,54(16):11169-11186.
[17]	KRESSE G, FURTHMULLER J . Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane- wave basis set. Computational Materials Science, 1996,6(1):15-50.
[18]	PERKEW J P, BURKE K, ERNZERHOF M . Generalized gradient approximation made simple. Physical Review Letters, 1996,77(18):3865-3868. DOI URL
[19]	KRESSE G, JOUBERT D . From ultrasoft pseudopotentials to the projector augmented-wave method. Physical Review B, 1999,59(3):1758-1775.
[20]	BLOCHL P E . Projector augmented-wave method. Physical Review B, 1994,50(24):17953-17979. DOI URL
[21]	HENKELMAN G, JUAO NSSON H . Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points. The Journal of Chemical Physics, 2000,113(22):9978-9985. DOI URL
[22]	MIKHAILIN V V, SPASSKY D A, KOLOBANOV V N , et al. Luminescence study of the LuBO₃ and LuPO₄ doped with RE ³⁺. Radiation Measurements, 2010,45(3-6):307-310.
[23]	WISNIEWSKI D, TAVERNIEER S, WOJTOWICZ A J , et al. LuPO₄:Nd and YPO₄:Nd—new promising VUV scintillation materials. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, 2002,486(1/2):239-243.
[24]	WISNIEWSKI D TAVERNIER S DORENBOS P , et al . VUV Scintillation of LuPO₄:Nd and YPO₄:Nd. IEEE Transactions on Nuclear Science, 2002,49(3):937-940.

第一原理研究LuPO₄中氧空位的性质

First Principles Study on the Property of O Vacancy in LuPO₄ Crystal

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 10

参考文献 24

相关文章 15

编辑推荐

Metrics

本文评价

[1]	吴玉豪, 彭仁赐, 程春玉, 杨丽, 周益春. Hf_xTa_1-_xC体系力学性能及熔化曲线的第一性原理研究[J]. 无机材料学报, 2024, 39(7): 761-768.
[2]	靳宇翔, 宋二红, 朱永福. 3d过渡金属单原子掺杂石墨烯缺陷电催化还原CO₂的第一性原理研究[J]. 无机材料学报, 2024, 39(7): 845-852.
[3]	王伟华, 张磊宁, 丁峰, 代兵, 韩杰才, 朱嘉琦, 贾怡, 杨宇. 铱衬底上金刚石外延形核与生长: 第一性原理计算[J]. 无机材料学报, 2024, 39(4): 416-422.
[4]	张宇晨, 陆知遥, 赫晓东, 宋广平, 朱春城, 郑永挺, 柏跃磊. 硫族MAX相硼化物的物相稳定性和性能预测[J]. 无机材料学报, 2024, 39(2): 225-232.
[5]	陈梦杰, 王倩倩, 吴成铁, 黄健. 基于DFT的描述符预测生物陶瓷的降解性[J]. 无机材料学报, 2024, 39(10): 1175-1181.
[6]	周云凯, 刁亚琪, 王明磊, 张宴会, 王利民. 聚苯胺改性Ti₃C₂(OH)₂抗氧化性的第一性原理计算研究[J]. 无机材料学报, 2024, 39(10): 1151-1158.
[7]	吴晓维, 张涵, 曾彪, 明辰, 孙宜阳. 杂化泛函HSE和PBE0计算CsPbI₃缺陷性质的比较研究[J]. 无机材料学报, 2023, 38(9): 1110-1116.
[8]	张守超, 陈洪雨, 刘洪飞, 杨羽, 李欣, 刘德峰. 6H-SiC中子辐照肿胀高温回复及光学特性研究[J]. 无机材料学报, 2023, 38(6): 678-686.
[9]	杨颖康, 邵怡晴, 李柏良, 吕志伟, 王路路, 王亮君, 曹逊, 吴宇宁, 黄荣, 杨长. Cl掺杂对CuI薄膜发光性能增强研究[J]. 无机材料学报, 2023, 38(6): 687-692.
[10]	杜剑宇, 葛琛. 光电人工突触研究进展[J]. 无机材料学报, 2023, 38(4): 378-386.
[11]	贾鑫, 李晋宇, 丁世豪, 申倩倩, 贾虎生, 薛晋波. Pd纳米颗粒协同氧空位增强TiO₂光催化CO₂还原性能[J]. 无机材料学报, 2023, 38(11): 1301-1308.
[12]	文志勤, 黄彬荣, 卢涛仪, 邹正光. 压力对PbTiO₃结构和热物性质影响的第一性原理研究[J]. 无机材料学报, 2022, 37(7): 787-794.
[13]	孙铭, 邵溥真, 孙凯, 黄建华, 张强, 修子扬, 肖海英, 武高辉. RGO/Al复合材料界面性质第一性原理研究[J]. 无机材料学报, 2022, 37(6): 651-659.
[14]	肖美霞, 李苗苗, 宋二红, 宋海洋, 李钊, 毕佳颖. 表面端基卤化Ti₃C₂ MXene应用于锂离子电池高容量电极材料的研究[J]. 无机材料学报, 2022, 37(6): 660-668.
[15]	袁罡, 马新国, 贺华, 邓水全, 段汪洋, 程正旺, 邹维. 平面应变对二维单层MoSi₂N₄能带结构和光电性质的影响[J]. 无机材料学报, 2022, 37(5): 527-533.