BaTiO<sub>3</sub>单晶表面结构及表面液体pH值的影响

郑旭; 李钊; 顾月良; 尹帅帅; 姜继超; 郭朴; 邱志勇; 李晓龙

doi:10.7498/aps.73.20240084

摘要

铁电材料是指在一定温度范围内具有自发极化, 且极化方向能被外加电场改变的材料, 而水是一种普遍存在的极性溶剂. 由于极性作用, 铁电材料与水及水溶液的界面存在着复杂的相互作用. 理解这些物理过程以及机制对于理论研究和实际应用都具有重要意义. 本工作利用同步辐射衍射技术研究了(001)方向极化BaTiO₃单晶的表面结构, 并且研究了不同pH值液体对表面结构的影响. 结果表明, BaTiO₃单晶含有一个电子密度较小的表面层, 并且由于极性的作用, BaTiO₃单晶表面吸附了2.6 nm的水层. 表面滴加纯水后, BaTiO₃的表面层结构没有明显的改变. 低温原位掠入射X射线衍射实验表明表面存在冰, 进一步验证表面吸附水层的存在. pH = 1的盐酸溶液也对BaTiO₃表面结构没有显著影响, 可能是由于酸性溶液能稳定原有的极化方向. 但pH = 13的NaOH溶液可以使表面层变厚, 可能由于碱性溶液可以使表面极化减弱, 从而改变表面退极化场以及表面层厚度.

关键词:

铁电极化 /
pH值 /
表面结构

Abstract

Ferroelectric material is a kind of material with spontaneous polarization, and water is a common polar solvent. Due to polarity, there are complex interactions at the interface between ferroelectric materials and water/aqueous solutions. Understanding these physical processes and mechanisms is of great significance for both theoretical research and practical applications. Herein, the surface structure of (001) orientated BaTiO₃ with (001) direction polarization single crystal is studied by synchrotron radiation diffraction technology, and the effects of liquids with different pH values on surface structure of BaTiO₃ single crystal was also investigated. The results show that BaTiO₃ single crystal contains a surface layer with a low electron density, and due to the effect of polarity, a 2.6 nm-thick water layer is adsorbed on the surface of BaTiO₃ single crystal. After adding deionized water on the surface, there is no significant change in the surface layer structure of BaTiO₃. Low temperature in-situ grazing incidence X-ray diffraction experiments indicate the presence of ice on the surface, further confirming the existence of adsorbed water layers on the surface. A hydrochloric acid solution with pH = 1 has no significant effect on the surface structure of BaTiO₃, either, which is possibly due to the ability of acidic solutions to stabilize the original polarization direction. However, an NaOH solution with a pH = 13 can thicken the surface layer, which possibly results from the weakening of surface polarization caused by alkaline solutions, thereby changing the surface depolarization field and surface layer thickness.

Keywords:

作者及机构信息

1.
大连理工大学材料科学与工程学院, 三束材料改性教育部重点实验室, 大连　116024

2.
中国科学院上海高等研究院, 上海同步辐射光源, 上海　201204

通信作者: 李晓龙, lixiaolong@zjlab.org.cn

基金项目: 国家自然科学基金(批准号: 12275344, 12304132)和国家重点研发计划(批准号: 2022YFA1603901)资助的课题.

Authors and contacts

1.
Key Laboratory of Materials Modification by Laser, Ion, and Electron Beams (Ministry of Education), School of Materials Science and Engineering, Dalian University of Technology, Dalian 116024, China

2.
Shanghai Synchrotron Radiation Facility (SSRF), Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201204, China

Corresponding author: Li Xiao-Long, lixiaolong@zjlab.org.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 12275344, 12304132) and the National Key Research and Development Program of China (Grant No. 2022YFA1603901).

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参考文献

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施引文献

图 1 GIXRD和XRR实验的衍射几何

Fig. 1. Diffraction geometry of GIXRD and XRR experiments

下载: 全尺寸图片幻灯片

图 2 BTO单晶的PFM和SEM图

Fig. 2. PFM and SEM images of BTO single crystal.

下载: 全尺寸图片幻灯片

图 3 BTO单晶的XRR图及拟合结果, 黑色方块为实验结果, 红线为拟合结果, 插图为电子密度随深度变化曲线　(a)未做任何处理; (b)表面滴加pH = 1的盐酸; (c)滴加去离子水; (d)滴加pH = 13的NaOH溶液

Fig. 3. XRR patterns and fitting results of BTO single crystal, black square represents experimental data, red curve represents fitting results. Inserts: electron density profile: (a) Without any treatment; (b) hydrochloric acid (pH = 1) on the surface; (c) deionized water on the surface; (d) NaOH solution (pH = 13) on the surface.

下载: 全尺寸图片幻灯片

图 4 BTO单晶面内晶格常数随入射角的变化

Fig. 4. In-plane lattice constants of BTO single crystal vary with incident angles.

下载: 全尺寸图片幻灯片

图 5 BTO单晶应变随深度变化图　(a)未做任何处理; (b)表面滴加pH = 1的盐酸; (c)滴加去离子水; (d)滴加pH = 13的NaOH溶液

Fig. 5. Strain variation with depth of BTO single crystal: (a) Without any treatment; (b) hydrochloric acid (pH = 1) on the surface; (c) deionized water on the surface; (d) NaOH solution (pH = 13) on the surface.

下载: 全尺寸图片幻灯片

图 6 低温下BTO单晶的GIXRD图

Fig. 6. GIXRD patterns of BTO single crystal at low temperatures.

下载: 全尺寸图片幻灯片

[1]	Chen L, Qian L M 2021 Friction 9 1 Google Scholar
[2]	Iwahori K, Watanabe S, Kawai M, Kobayashi K, Yamada H, Matsushige K 2003 J. Appl. Phys. 93 3223 Google Scholar
[3]	Geneste G, Dkhil B 2009 Phys. Rev. B 79 235420 Google Scholar
[4]	Domingo N, Pach E, Cordero-Edwards K, Perez-Dieste V, Escudero C, Verdaguer A 2019 Phys. Chem. Chem. Phys. 21 4920 Google Scholar
[5]	Li X, Wang B C, Zhang T Y, Su Y J 2014 J. Phys. Chem. C 118 15910 Google Scholar
[6]	Efe I, Spaldin N A, Gattinoni C 2021 J. Chem. Phys. 154 024702 Google Scholar
[7]	Chornik B, Fuenzalida V A, Grahmann C R, Labbe R 1997 Vacuum 48 161 Google Scholar
[8]	Wegmann M, Watson L, Hendry A 2004 J. Am. Ceram. Soc. 87 371 Google Scholar
[9]	Fuenzalida V M, Pilleux M E, Eisele I 1999 Vacuum 55 81 Google Scholar
[10]	Wang J L, Gaillard F, Pancotti A, Gautier B, Niu G, Vilquin B, Pillard V, Rodrigues G L M P, Barrett N 2012 J. Phys. Chem. C 116 21802 Google Scholar
[11]	Lee H, Kim T H, Patzner J J, Lu H, Lee J W, Zhou H, Chang W, Mahanthappa M K, Tsymbal E Y, Gruverman A, Eom C B 2016 Nano Lett. 16 2400 Google Scholar
[12]	Song W, Salvador P A, Rohrer G S 2018 Surface Sci. 675 83 Google Scholar
[13]	Shin J, Nascimento V B, Geneste G, Rundgren J, Plummer E W, Dkhil B, Kalinin S V, Baddorf A P 2009 Nano Lett. 9 3720 Google Scholar
[14]	Pierre-Marie D, Bruno D, Céline D 2020 Phys. Rev. B 101 075410 Google Scholar
[15]	Marra W C, Eisenberger P, Cho A Y 1979 J. Appl. Phys. 50 6927 Google Scholar
[16]	Dosch H, Batterman B W, Wack D C 1986 Phys. Rev. Lett. 56 1144 Google Scholar
[17]	Marti X, Ferrer P, Herrero-Albillos J, Narvaez J, Holy V, Barrett N, Alexe M, Catalan G 2011 Phys. Rev. Lett. 106 236101 Google Scholar
[18]	Song C Y, Gao J C, Liu J C, Yang Y B, Tian C F, Hong J W, Weng H M, Zhang J X 2020 ACS Appl. Mater. Interfaces 12 4150 Google Scholar
[19]	Barabanova E V, Ivanova A I, Malyshkina O V, Vinogradova Y K, Akbaeva G M 2021 Ferroelectrics 574 37 Google Scholar
[20]	Li X L, Lu H B, Li M, Mai Z H, Kim H, Jia Q J 2008 Appl. Phys. Lett. 92 012902 Google Scholar
[21]	Li X L, Lu H B, Li M, Mai Z H, Kim H 2008 J. Appl. Phys. 103 054109 Google Scholar
[22]	Yang T Y, Zhang X M, Chen B, Guo H Z, Jin K J, Wu X S, Gao X Y, Li Z, Wang C, Li X L 2017 ACS Appl. Mater. Interfaces 9 5600 Google Scholar
[23]	Lee D, Yoon A, Jang S Y, Yoon J G, Chung J S, Kim M, Scott J F, Noh T W 2011 Phys. Rev. Lett. 107 057602 Google Scholar
[24]	Kalinin S V, Bonnell D A 2001 Phys. Rev. B 63 125411 Google Scholar
[25]	Tian Y, Wei L Y, Zhang Q H, Huang H B, Zhang Y L, Zhou H, Ma F J, Gu L, Meng S, Chen L Q, Nan C W, Zhang J X 2018 Nat. Commun. 9 3809 Google Scholar

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BaTiO₃单晶表面结构及表面液体pH值的影响