高分子辅助沉积法制备LaNiO3外延导电薄膜

doi:10.15541/jim20210271

无机材料学报 ›› 2022, Vol. 37 ›› Issue (5): 561-566.DOI: 10.15541/jim20210271 CSTR: 32189.14.10.15541/jim20210271

所属专题：【信息功能】纪念殷之文先生诞辰105周年虚拟学术专辑

高分子辅助沉积法制备LaNiO₃外延导电薄膜

杨柱¹^,²(), 郭少波¹(), 蔡恒辉¹^,², 董显林¹^,²^,³, 王根水¹^,²^,³()

1. 中国科学院上海硅酸盐研究所, 无机功能材料与器件实验室, 上海 200050
2. 中国科学院大学材料科学与光电子工程中心, 北京 100049
3. 中国科学院上海硅酸盐研究所, 高性能陶瓷和超微结构国家重点实验室, 上海 200050

收稿日期:2021-04-26 修回日期:2021-05-23 出版日期:2022-05-20 网络出版日期:2021-07-20
通讯作者: 王根水, 研究员. E-mail: genshuiwang@mail.sic.ac.cn; 郭少波, 高级工程师. E-mail: guoshaobo@mail.sic.ac.cn
作者简介:杨柱(1996–), 男, 硕士研究生. E-mail: yangzhu@student.sic.ac.cn

Preparation of Epitaxial Metallic LaNiO₃ Thin Film by Polymer Assisted Deposition

YANG Zhu¹^,²(), GUO Shaobo¹(), CAI Henghui¹^,², DONG Xianlin¹^,²^,³, WANG Genshui¹^,²^,³()

1. Key Laboratory of Inorganic Functional Materials and Devices, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
3. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

Received:2021-04-26 Revised:2021-05-23 Published:2022-05-20 Online:2021-07-20
Contact: ANG Genshui, professor. E-mail: genshuiwang@mail.sic.ac.cn; GUO Shaobo, senior engineer. E-mail: guoshaobo@mail.sic.ac.cn
About author:YANG Zhu (1996–), male, Master candidate. E-mail: yangzhu@student.sic.ac.cn
Supported by:
National Natural Science Foundation of China(11774366);International Partnership Program of Chinese Academy of Sciences(GJHZ1821)

摘要/Abstract

摘要：

近年来LaNiO₃(LNO)作为铁电超晶格、超导异质结和催化剂材料引起了广泛关注。本研究采用简便、低成本的高分子辅助沉积法(Polymer Assisted Deposition, PAD), 在(001)取向的SrTiO₃(STO)单晶衬底上制备了导电性能优异的LNO外延薄膜, 并对其进行各种结构和电学表征。摇摆曲线半高宽为0.38°, 表明LNO薄膜结晶度良好。高分辨XRD的φ扫描进一步证实LNO薄膜在STO衬底上异质外延生长。原位变温XRD测试进一步表征了LNO薄膜的外延生长过程。结果表明, 聚合物分解之后金属阳离子在单晶基体上有序释放并外延结晶。XPS结果表明, 采用PAD制备的LaNiO₃薄膜不存在氧空位。薄膜表面光滑, 粗糙度为0.67 nm。在10~300 K温度区间内的变温电阻率表明LNO薄膜具有良好的导电性能。上述结果表明：PAD制备的LaNiO₃薄膜具有较好的综合性能, PAD在制备外延功能薄膜材料方面具有很大的潜力。

关键词: LaNiO₃, 导电薄膜, 高分子辅助沉积法, 外延

Abstract:

LaNiO₃ (LNO), as a promising material in ferroelectric super lattices, super conductive heterostructures and catalysts has recently attracted great interest. Herein, a facile and low-cost polymer assisted deposition (PAD) method is established to prepare epitaxial LNO thin films on (001) orientated SrTiO₃ (STO) with excellent conductivity. Various structural and electrical characterizations of the film were investigated. The film has good crystallinity with a full-width at half-maximum value of 0.38° from the rocking curve for the (002) reflection. High resolution XRD φ-scans further confirmed the heteroepitaxial growth of LNO film on STO substrate. There are four peaks separated by 90°, showing that the LNO thin film is cubic-on-cubic grown on STO substrate. In-situ high temperature XRD measurement showed epitaxial growth of LNO thin film on STO substrate. Metal cations could be released orderly on the monocrystalline substrate and epitaxial crystallization occurs after decomposition of polymer. XPS results indicated that LaNiO₃ thin film fabricated by PAD was stoichiometric without oxygen vacancy. The atomic force microscopy analysis showed that the smooth surface with root-mean-square surface roughness was 0.67 nm. The resistivity as functions of temperature revealed that it has good conductivity from 10 K to 300 K. All results demonstrate that the LaNiO₃ thin films deposited by PAD have better comprehensive performance, indicating that PAD method has great potential for preparing epitaxial functional thin film materials.

Key words: LaNiO₃, conductive film, polymer assisted deposition, epitaxial

中图分类号:

TQ174

杨柱, 郭少波, 蔡恒辉, 董显林, 王根水. 高分子辅助沉积法制备LaNiO₃外延导电薄膜[J]. 无机材料学报, 2022, 37(5): 561-566.

YANG Zhu, GUO Shaobo, CAI Henghui, DONG Xianlin, WANG Genshui. Preparation of Epitaxial Metallic LaNiO₃ Thin Film by Polymer Assisted Deposition[J]. Journal of Inorganic Materials, 2022, 37(5): 561-566.

图/表 5

Fig. 1 Charaterization of as-prepared LNO film (a) HRXRD patterns of the LNO films; (b) Rocking-curve of the (002) LNO reflection; (c) φ-scans from (202) reflection of LNO and (202) of STO; (d) 3D AFM micrograph of LNO film; (e) Bright-field cross-sectional TEM image of LNO film on STO substrate; (f) Cross-sectional HRTEM image of the interface between LNO and STO

Fig. 2 In-situ XRD patterns of LNO film on STO substrate at different temperatures

Fig. 3 Survey (a), La3d (b), Ni2p (c) and O1s (d) XPS spectra of LaNiO3

Table 1 Summary of the parameters of LNO films grown by different methods

Method	Substrate	Orientation	d/nm	ρ_{300 K}/ (μΩ·cm)	Ref.
SCD	SrTiO₃	Preferred orientation	100	340	[31]
RF-MS	LaAlO₃	Epitaxial	9	~150	[28]
MBE	SrTiO₃	Epitaxial	36	~90	[29]
PLD	SrTiO₃	Epitaxial	50-60	100	[30]
PAD	SrTiO₃	Epitaxial	25	160	This work

Fig. 4 Temperature dependence of resistivity of 25 nm LNO film on STO substrate

参考文献 31

[1]	PONTES D S L, PONTES F M, CHIQUITO A J,et al. Investigation of the structural, optical and dielectric properties of highly (100)-oriented (Pb_0.60Ca_0.20Sr_0.20)TiO₃ thin films on LaNiO₃ bottom electrode. Materials Science and Engineering: B, 2014,185:123-128.
[2]	PONTES D S L, CAPELI R A, GARZIM M L,et al. Structural, microstructural, optical and electrical properties of (Pb,Ba,Sr)TiO₃ films growth on conductive LaNiO₃-coated LaAO₃( 100) and Pt/Ti/SiO₂/Si substrates. Materials Letters, 2014,121:93-96.
[3]	ZHU J, ZHENG L, ZHANG Y,et al. Fabrication of epitaxial conductive LaNiO₃ films on different substrates by pulsed laser ablation. Materials Chemistry and Physics, 2006,100(2/3):451-456.
[4]	CHEN M S, WU T B, WU J M. Effect of textured LaNiO₃ electrode on the fatigue improvement of Pb(Zr_0.53Ti_0.47)O₃ thin films. Applied Physics Letters, 1996,68(10):1430-1432.
[5]	CHAE B G, YANG Y S, LEE S H,et al. Comparative analysis for the crystalline and ferroelectric properties of Pb(Zr,Ti)O₃ thin films deposited on metallic LaNiO₃ and Pt electrodes. Thin Solid Films, 2002,410(1/2):107-113.
[6]	LI W L, ZHANG T D, XU D,et al. LaNiO₃ seed layer induced enhancement of piezoelectric properties in (100)-oriented (1-x)BZT-xBCT thin films. Journal of the European Ceramic Society, 2015,35(7):2041-2049.
[7]	WANG J, NEATON J B, ZHENG H,et al. Epitaxial BiFeO₃ multiferroic thin film heterostructures. Science, 2003,299(5613):1719-1722.
[8]	LEE J H, MURUGAVEL P, RYU H,et al. Epitaxial stabilization of a new multiferroic hexagonal phase of TbMnO₃ thin films. Advanced Materials, 2006,18(23):3125-3129.
[9]	SCHERWITZL R, GARIGLIO S, GABAY M,et al. Metal- insulator transition in ultrathin LaNiO₃ films. Physical Review Letters, 2011,106(24):246403.
[10]	LIU P, NING X. Anisotropy of core-level spectra and the correlation with transport properties of epitaxial lanthanum nickel oxide thin films. Physica B: Condensed Matter, 2020,589:412199.
[11]	CHEN P, XU S Y, ZHOU W Z,et al. In situ reflection high-energy electron diffraction observation of epitaxial LaNiO₃ thin films. Journal of Applied Physics, 1999,85(5):3000-3002.
[12]	MAMBRINI G P, LEITE E R, ESCOTE M T,et al. Structural, microstructural, and transport properties of highly oriented LaNiO₃ thin films deposited on SrTiO₃(100) single crystal. Journal of Applied Physics, 2007,102(4):043708.
[13]	CHO C R, PAYNE D A, CHO S L. Solution deposition and heteroepitaxial crystallization of LaNiO₃ electrodes for integrated ferroelectric devices. Applied Physics Letters, 1997,71(20):3013-3015.
[14]	FEI L, NAEEMI M, ZOU G,et al. Chemical solution deposition of epitaxial metal-oxide nanocomposite thin films. Chemical Record, 2013,13(1):85-101.
[15]	GOH P C, YAO K, CHEN Z. Reaction mechanisms of ethylenediaminetetraacetic acid and diethanolamine in the precursor solution for producing (K, Na)NbO₃ thin films with outstanding piezoelectric properties. The Journal of Physical Chemistry C, 2012,116(29):15550-15556.
[16]	JIA Q X, MCCLESKEY T M, BURRELL A K,et al. Polymer- assisted deposition of metal-oxide films. Nature Materials, 2004,3(8):529-532.
[17]	LIN Y, LEE J S, WANG H,et al. Structural and dielectric properties of epitaxial Ba₁-_xSr_xTiO₃ films grown on LaAlO₃ substrates by polymer-assisted deposition. Applied Physics Letters, 2004,85(21):5007-5009.
[18]	LUO H M, WANG H Y, BI Z X,et al. Epitaxial ternary nitride thin films prepared by a chemical solution method. Journal of the American Chemical Society, 2008,130(46):15224-15225.
[19]	ZOU G, LUO H, ZHANG Y,et al. A chemical solution approach for superconducting and hard epitaxial NbC film. Chemical Communications, 2010,46(41):7837-7839.
[20]	KUMAH D P, NGAI J H, KORNBLUM L. Epitaxial oxides on semiconductors: from fundamentals to new devices. Advanced Functional Materials, 2019,30(18):1901597.
[21]	BURRELL A K, MARK MCCLESKEY T, JIA Q X. Polymer assisted deposition. Chemical Communications, 2008,11(11):1271-1277.
[22]	VILA-FUNGUEIRIÑO J M, RIVAS-MURIAS B, RUBIO- ZUAZO J,et al. Polymer assisted deposition of epitaxial oxide thin films. Journal of Materials Chemistry C, 2018,6(15):3834-3844.
[23]	WANG H, FRONTERA C, HERRERO-MARTIN J,et al. Aqueous chemical solution deposition of functional double perovskite epitaxial thin films. Chemistry, 2020,26(42):9338-9347.
[24]	YANG E H, MOON D J. Synthesis of LaNiO₃ perovskite using an EDTA-cellulose method and comparison with the conventional pechini method: application to steam CO₂ reforming of methane. RSC Advances, 2016,6(114):112885-112898.
[25]	WANG G, LING Y, LU X,et al. A mechanistic study into the catalytic effect of Ni(OH)₂ on hematite for photoelectrochemical water oxidation. Nanoscale, 2013,5(10):4129-4133.
[26]	TSUBOUCHI K, OHKUBO I, KUMIGASHIRA H,et al. Epitaxial growth and surface metallic nature of LaNiO₃ thin films. Applied Physics Letters, 2008,92(26):262109.
[27]	HE B, WANG Z. Effect of substrate temperature on microstructure and electrical properties of LaNiO₃ films grown on SiO₂/Si substrates by pulsed laser deposition under a high oxygen pressure. Applied Physics A, 2016,122(10):905.
[28]	SON J, MOETAKEF P, LEBEAU J M,et al. Low-dimensional mott material: transport in ultrathin epitaxial LaNiO₃ films. Applied Physics Letters, 2010,96(6):062114.
[29]	DOBIN A Y, NIKOLAEV K R, KRIVOROTOV I N,et al. Electronic and crystal structure of fully strained LaNiO₃ films. Physical Review B, 2003,68(11):113408.
[30]	ZHU M, KOMISSINSKIY P, RADETINAC A,et al. Effect of composition and strain on the electrical properties of LaNiO₃ thin films. Applied Physics Letters, 2013,103(14):141902.
[31]	MIYAKE S, FUJIHARA S, KIMURA T. Characteristics of oriented LaNiO₃ thin films fabricated by the Sol-Gel method. Journal of the European Ceramic Society, 2001,21(10/11):1525-1528.

高分子辅助沉积法制备LaNiO₃外延导电薄膜

Preparation of Epitaxial Metallic LaNiO₃ Thin Film by Polymer Assisted Deposition

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 5

参考文献 31

相关文章 15

编辑推荐

Metrics

本文评价

[1]	安瑕, 许晟瑞, 陶鸿昌, 苏华科, 杨赫, 许钪, 谢磊, 贾敬宇, 张进成, 郝跃. Ar离子注入蓝宝石衬底诱导成核的高质量GaN外延[J]. 无机材料学报, 2025, 40(1): 91-96.
[2]	卢灏, 许晟瑞, 黄永, 陈兴, 徐爽, 刘旭, 王心颢, 高源, 张雅超, 段小玲, 张进成, 郝跃. 等离子体增强原子层沉积AlN外延单晶GaN研究[J]. 无机材料学报, 2024, 39(5): 547-553.
[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]	任冠源, 李宜冠, 丁冬海, 梁瑞虹, 周志勇. CaBi₂Nb₂O₉铁电薄膜的生长取向调控和性能研究[J]. 无机材料学报, 2024, 39(11): 1228-1234.
[5]	齐占国, 刘磊, 王守志, 王国栋, 俞娇仙, 王忠新, 段秀兰, 徐现刚, 张雷. GaN单晶的HVPE生长与掺杂进展[J]. 无机材料学报, 2023, 38(3): 243-255.
[6]	张超逸, 唐慧丽, 李宪珂, 王庆国, 罗平, 吴锋, 张晨波, 薛艳艳, 徐军, 韩建峰, 逯占文. 新型GaN与ZnO衬底ScAlMgO₄晶体的研究进展[J]. 无机材料学报, 2023, 38(3): 228-242.
[7]	王杨, 朱嘉琦, 扈忠波, 代兵. 铱衬底上异质外延单晶金刚石: 过程与机理[J]. 无机材料学报, 2019, 34(9): 909-917.
[8]	郭钰, 彭同华, 刘春俊, 杨占伟, 蔡振立. 4H-SiC外延层中堆垛层错与衬底缺陷的关联性研究[J]. 无机材料学报, 2019, 34(7): 748-754.
[9]	叶长辉, 顾瑜佳, 王贵欣, 毕丽丽. 银纳米线透明导电薄膜的失效机理研究[J]. 无机材料学报, 2019, 34(12): 1257-1264.
[10]	孙洪君, 王敏焕, 边继明, 苗丽华, 章俞之, 骆英民. MBE技术蓝宝石衬底上生长VO₂薄膜及其太赫兹和金属-绝缘体相变特性研究[J]. 无机材料学报, 2017, 32(4): 437-442.
[11]	王锦, 陶科, 李国峰, 梁科, 蔡宏琨. 氢气氛退火对硅上低温外延制备的硅锗薄膜性能的影响[J]. 无机材料学报, 2017, 32(2): 191-196.
[12]	韩霜霜, 刘莉月, 单永奎, 杨帆, 李德增. 石墨烯/纳米减反结构复合透明导电薄膜的研究[J]. 无机材料学报, 2017, 32(2): 197-202.
[13]	刘广政, 徐波, 叶晓玲, 刘峰奇, 王占国. 四步法制备高质量硅基砷化镓薄膜[J]. 无机材料学报, 2016, 31(11): 1263-1268.
[14]	吕坤, 祝柏林, 李珂, 胡文超, 谢铭, 吴隽. 氢气与Cu中间层对GZO薄膜光电性能的影响[J]. 无机材料学报, 2014, 29(5): 493-497.
[15]	崔林, 汪桂根, 张化宇, 周福强, 韩杰才. 用于GaN基发光二极管的蓝宝石图形衬底制备进展[J]. 无机材料学报, 2012, 27(9): 897-905.