硅酸盐学报

有序氧空位调控BiFeO₃薄膜的极化与光学特性

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耿皖荣 ¹ , 江亦潇 ² , 朱银莲 ¹^,³ , 马秀良 ¹^,⁴^,⁵

硅酸盐学报 | 面向新一代信息技术应用的铁电薄膜与器件专题—研究论文 2025,53(9): 2421-2429

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硅酸盐学报 |面向新一代信息技术应用的铁电薄膜与器件专题—研究论文 2025 , 53 (9) : 2421 -2429

有序氧空位调控BiFeO₃薄膜的极化与光学特性

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耿皖荣¹, 江亦潇², 朱银莲¹^,³, 马秀良¹^,⁴^,⁵

作者信息

^1．松山湖材料实验室大湾区显微科学与技术研究中心，广东东莞 523808

^2．中国科学院金属研究所，沈阳 110016

^3．湖南科技大学，湖南湘潭 411201

^4．中国科学院物理研究所，北京 100190

^5．粤港澳大湾区量子科学中心，广东深圳 518102

通讯作者:

马秀良（1964—），男，博士，研究员。

作者简介:

耿皖荣（1992—），女，博士，副研究员。

Ordered Oxygen Vacancy Modulated Polarization and Optical Properties in BiFeO₃ Thin Films

Wan-Rong GENG¹, Yixiao JIANG², Yin-Lian ZHU¹^,³, Xiu-Liang MA¹^,⁴^,⁵

Affiliations

^1.Bay Area Center for Electron Microscopy, Songshan Lake Materials Laboratory, Dongguan 523808, Guangdong, China

^2.Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China

^3.Hunan University of Science and Technology, Xiangtan 411201, Hunan, China

^4.Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China

^5.Quantum Science Center of Guangdong-HongKong-Macau Greater Bay Area (Guangdong), Shenzhen 510290, Guangdong, China

Corresponding Author:

MA Xiuliang (1964-), male, Ph.D., Professor. E-mail: xlma@sslab.org.cn

GENG Wanrong (1992-), female, Ph.D., Associate Professor. E-mail: gengwanrong@sslab.org.cn

出版时间: 2025-09-20 doi: 10.14062/j.issn.0454-5648.20250308

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摘要

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氧空位作为一种结构序参量，通过与应变、极化和磁化的协同作用及竞争调控强关联氧化物的功能特性。通过引入可调控的氧空位有序面，利用像差校正透射电子显微镜系统地研究了其对多铁性BiFeO₃薄膜铁电极化与光响应特性的影响机制。研究发现，通过调节退火氧分压和覆盖层工艺，可在BiFeO₃薄膜中实现氧空位有序面的引入和对其密度的精确调控，表现为显著的晶格膨胀、Fe³⁺/Fe²⁺混合价态和稳定的尾-尾极化组态，进而提高BiFeO₃薄膜的光吸收性能。本工作阐明了多铁BiFeO₃薄膜中氧空位有序面对铁电极化和光响应性能的调控行为。

关键词

铁酸铋薄膜 / 氧空位有序面 / 光吸收 / 第一性原理计算

Abstract

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Introduction

Multiferroic BiFeO₃ (BFO) exhibits coupled ferroelectric, antiferromagnetic, and ferroelastic orders at room temperature, enabling unique optoelectronic properties such as switchable photovoltaic effects and polarization-driven carrier separation. The multi-valance of Fe element in BFO also implies its potential to engineer the bandgap and conductivity to enhance the photoelectric properties. Besides, the large remnant ferroelectric polarization in BFO offers the opportunity of bulk photovoltaic effect, promising to develop the optoelectronic devices based on the unique optical and multiferroic properties. While defects like oxygen vacancies are known to critically influence functional properties in oxides, especially the BFO films. The oxygen vacancies are proved to influence the electronic and magnetic properties, electromechanical response and resistive switching. Furthermore, the concentration of oxygen vacancies is clarified to be influenced by the annealed conditions, which in turn tune the photoresponse of BFO thin films. However, previous studies mainly focus on the influence of the oxygen vacancies as the point defects on properties and the atomic-resolved analyses of oxygen vacancies behavior are lacking. Here, by combining advanced STEM, UV-Vis, XRD and first-principles calculations, we systematically investigate oxygen-vacancy-engineered BFO thin films to reveal how ordered vacancy planes modulate lattice structure, create charged domain walls, reduce bandgaps and improve UV-visible absorption property, thereby demonstrating a defect-property correlation crucial for designing multifunctional devices.

Methods

BFO polycrystalline ceramic target (1% Bi-enriched), SrTiO₃ (STO) ceramic target, and commercial single-crystal substrates of NdGaO₃ (NGO) (110)_O and STO (001) were purchased from Hefei Kejing Materials Technology Co., Ltd. BFO and BFO/STO films were grown on NGO (110)_O substrates via pulsed laser deposition (PLD) using a Coherent ComPex PRO 201 F KrF excimer laser (λ = 248 nm). The substrates were preheated to 850 ℃ for 20 min and cooled to deposition temperature at 5 ℃/min. A 1% Bi-enriched BFO target was pre-sputtered for 20 min. The deposition parameters of 6 Hz repetition rate, 800 ℃ substrate temperature, 370 mJ laser energy were used to fabricate the films. Post-deposition annealing at 800 ℃ for 20 min was followed by cooling to 200 ℃ at a rate of 5 ℃/min and natural cooling to RT under 200 Torr O₂ partial pressures. Four film systems were prepared by varying O₂ partial pressures:1) BFO film: growing at 90 mTorr, annealing at 200 Torr; 2) BFO film: growing at 90 mTorr, annealing at 120 mTorr; 3) BFO/STO film: BFO layer growing at 90 mTorr, STO capping layer growing at 70 mTorr, both layers were annealed at 120 mTorr; 4) BFO/STO film: growing/annealing at 0.06 mTorr.

Cross-sectional TEM specimens were prepared using a ThermoFisher Helios 5UX FIB system with sequential steps: C/W protective layer deposition, trenching, lift-out, thinning (30 kV/90 pA → 8 kV/47 pA), and amorphous layer removal (5 kV/47 pA → 2 kV/47 pA). The atomic-resolved HAADF-STEM images were acquired on ThermoFisher Spectra 300 (300 kV, 25 mrad convergence, 71-200 mrad collection angles) with drift correction (DCFI in Velox). The strain analysis was performed using GPA via Gatan GMS3 software and the atomic positions were determined by 2D Gaussian fitting in MATLAB software. The UV-Vis measurements were performed in JASCO V-770. The RSMs were collected on Bruker D8 Advance (Cu K_α, λ = 1.5406 Å). First-principles calculations were based on the density functional theory (DFT) calculation and performed with the Vienna ab initio simulation package (VASP).

Results and discussion

A series of BFO films were fabricated by modulating the oxygen environment to introduce the high-density oxygen vacancies. Using the Cs-STEM, the oxygen vacancy ordered plane was determined in BFO film annealed under the oxygen partial pressure of 120 mTorr, which displayed as the out-of-plane lattice expansion. Besides, the charged oxygen vacancy ordered plane would influence the surrounding polarization directions, stabilizing the tail-tail polarization distribution. By changing the annealed oxygen partial pressure and growing the capping layers, the concentration of oxygen vacancy ordered planes was evidently modulated, further extending the ultraviolet-visible absorption property of the BFO films. First-principles calculations revealed that the introduction of high-density oxygen vacancies could generate the vacancy-induced energy levels between the conduction and valance bands and thus reduce the bandgaps of BFO. The result was consistent with the UV-visible absorption measurement results.

Conclusion

The oxygen vacancy ordered planes were introduced in BiFeO₃ film systems by controllable growth methods. Its concentration was tunable by decreasing the annealed oxygen partial pressure and/or growing capping layers. Obvious lattice expansion was observed in BFO films by the existence of oxygen vacancy ordered planes. Besides, the polarization configuration in BFO film was modulated by the electrostatic potential of positively charged oxygen vacancy layer, accompanying the formation of tail-to-tail polarization configuration. The introduced oxygen vacancy ordered planes also had further improved the optical absorption properties of BFO films. Our results provide a further insight into the interaction between oxygen vacancy ordered planes with the ferroelectric polarization and the optical properties in multiferroic oxides and facilitate the design of nanoscale photoelectronic devices and ferroelectric solar cells.

Key words

bismuth ferrite thin films / oxygen vacancy ordered planes / light absorption / first-principles calculations

引用本文

耿皖荣, 江亦潇, 朱银莲, 马秀良. 有序氧空位调控BiFeO₃薄膜的极化与光学特性. 硅酸盐学报, 2025 , 53 (9) : 2421 -2429 . DOI: 10.14062/j.issn.0454-5648.20250308

Wan-Rong GENG, Yixiao JIANG, Yin-Lian ZHU, Xiu-Liang MA. Ordered Oxygen Vacancy Modulated Polarization and Optical Properties in BiFeO₃ Thin Films[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (9) : 2421 -2429 . DOI: 10.14062/j.issn.0454-5648.20250308

基金

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国家自然科学基金(52201018; 51971223)
广东省基础与应用基础研究基金(2021A1515110291; 2023A1515012796)
广东省量子科学战略计划(GDZX2202001; GDZX2302001; GDZX2402001)
松山湖科学城显微科学与技术开放基金(202401202)

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2025年第53卷第9期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250308

接收时间：2025-04-16
首发时间：2026-10-21
出版时间：2025-09-20

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出版历史

收稿日期：2025-04-16
修回日期：2025-04-30

基金

国家自然科学基金(52201018; 51971223)

广东省基础与应用基础研究基金(2021A1515110291; 2023A1515012796)

广东省量子科学战略计划(GDZX2202001; GDZX2302001; GDZX2402001)

松山湖科学城显微科学与技术开放基金(202401202)

作者信息

^1．松山湖材料实验室大湾区显微科学与技术研究中心，广东东莞 523808

^2．中国科学院金属研究所，沈阳 110016

^3．湖南科技大学，湖南湘潭 411201

^4．中国科学院物理研究所，北京 100190

^5．粤港澳大湾区量子科学中心，广东深圳 518102

通讯作者:

马秀良（1964—），男，博士，研究员。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250308

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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