浓度梯度掺杂实现BiFeO3薄膜自极化

doi:10.15541/jim20230278

无机材料学报 ›› 2024, Vol. 39 ›› Issue (1): 99-106.DOI: 10.15541/jim20230278

浓度梯度掺杂实现BiFeO₃薄膜自极化

戴乐¹(), 刘洋¹, 高轩¹, 王书豪¹, 宋雅婷¹, 唐明猛¹, 刘丽莎¹(), 汪尧进¹()

1.南京理工大学材料科学与工程学院, 南京 210094
2.罗斯国家科学院材料科学与应用研究中心, 明斯克 220072, 白俄罗斯

收稿日期:2023-06-12 修回日期:2023-08-07 出版日期:2024-01-20 网络出版日期:2023-10-07
通讯作者: 汪尧进, 教授. E-mail: yjwang@njust.edu.cn;
刘丽莎, 教授. E-mail: lishaliu@njust.edu.cn
作者简介:戴乐(1998-), 女, 硕士研究生. E-mail: DL_2323@163.com

Self-polarization Achieved by Compositionally Gradient Doping in BiFeO₃ Thin Films

DAI Le¹(), LIU Yang¹, GAO Xuan¹, WANG Shuhao¹, SONG Yating¹, TANG Mingmeng¹, DMITRY V Karpinsky², LIU Lisha¹(), WANG Yaojin¹()

1. School of Materials Science and Engineering, Nanjing University of Science and Technology, Nanjing 210094, China
2. entific and Practical Centre for Materials Research, National Academy of Sciences of Belarus, Minsk 220072, Belarus

Received:2023-06-12 Revised:2023-08-07 Published:2024-01-20 Online:2023-10-07
Contact: WANG Yaojin, professor. E-mail: yjwang@njust.edu.cn;
LIU Lisha, professor. E-mail: lishaliu@njust.edu.cn
About author:DAI Le (1998-), female, Master candidate. E-mail: DL_2323@163.com
Supported by:
National Natural Science Foundation of China(52102133);Natural Science Foundation of Jiangsu Province, China(BK20210354);Fundamental Research Funds for the Central Universities(30921011217);Young Elite Scientists Sponsorship Program by CAST(2021-2023QNRC001)

摘要/Abstract

摘要：

BiFeO₃是一种非常有前途的无铅铁电材料, 与大多数传统铁电材料相比, 它具有更大的极化和更高的居里温度, 为高温应用提供了可能。受到衬底强烈的夹持效应、较大的矫顽场和漏电流的影响, BiFeO₃薄膜难以被极化。自极化是解决这一问题的可行方法。本研究采用溶胶-凝胶法在Pt(111)/Ti/SiO₂/Si衬底上生长了BiFeO₃薄膜, 向上梯度薄膜(从衬底BiFeO₃过渡到薄膜表面Bi_0.80Ca_0.20FeO_2.90)以及向下梯度薄膜(从衬底Bi_0.80Ca_0.20FeO_2.90过渡到薄膜表面BiFeO₃)。通过细致地调控薄膜内部缺陷的定向分布形成内置电场，从而导致薄膜具有自极化特性。压电力显微镜结果表明：在BiFeO₃薄膜中, Ca的梯度方向可以调控自极化的方向。此外, 类似二极管的单向导通特性验证了薄膜的自极化是由Ca的浓度梯度掺杂导致。X射线光电子能谱结果表明, 氧空位的梯度分布导致的内置电场可能是造成自极化现象的原因。本研究为实现铁电薄膜的自极化提供了一种新的策略, 并在以自极化的内置电场为驱动, 提高光伏或光敏器件性能方面具有潜在的应用前景。

关键词: 自极化, 梯度掺杂, 铁酸铋薄膜, 溶胶-凝胶法

Abstract:

BiFeO₃ is a highly promising lead-free ferroelectric material, surpassing most conventional ferroelectric materials in terms of the polarization and Curie temperature, offering a pathway for potential applications at elevated temperatures. Nevertheless, challenges arise due to strong clamping effect of substrate, large coercive fields, and high leakage currents, causing BiFeO₃ films difficult to be polarized. The implementation of self-polarization presents a viable solution. Herein, we prepared BiFeO₃, up-graded films (which transition from BiFeO₃ to Bi_0.80Ca_0.20FeO_2.90 from the substrate to the film surface), and down-graded films (which transition from Bi_0.80Ca_0.20FeO_2.90 to BiFeO₃ from the substrate to the film surface) using the Sol-Gel method on Pt(111)/Ti/SiO₂/Si substrates. After directional distribution of defects within the film being carefully modulated, the BiFeO₃ films are self-polarization when induced by build-in electric field. Piezoresponse force microscopy show that the up-graded and down-graded self-polarization behavior can be modulated by gradient direction of Ca in BiFeO₃ thin films. Moreover, diode-like current-voltage signature verifies the composition gradient-induced self-polarization. The X-ray photoelectron spectroscopy results indicate that the polarization orientation mechanism may arise from the internal electric field attributed to the gradient distribution of oxygen vacancy. This work provides a new strategy to achieve self-polarization in ferroelectric thin films, as well potential novel application in improving the performance of photovoltaic or photosensitive devices as assisted by internal field via self-aligned ferroelectric polarization.

Key words: self-polarization, gradient doping, bismuth ferrite film, Sol-Gel method

中图分类号:

TB383

戴乐, 刘洋, 高轩, 王书豪, 宋雅婷, 唐明猛, 刘丽莎, 汪尧进. 浓度梯度掺杂实现BiFeO₃薄膜自极化[J]. 无机材料学报, 2024, 39(1): 99-106.

DAI Le, LIU Yang, GAO Xuan, WANG Shuhao, SONG Yating, TANG Mingmeng, DMITRY V Karpinsky, LIU Lisha, WANG Yaojin. Self-polarization Achieved by Compositionally Gradient Doping in BiFeO₃ Thin Films[J]. Journal of Inorganic Materials, 2024, 39(1): 99-106.

图/表 10

Fig. 1 (a-c) Schematic drawings of structures; Ferroelectric domains illustrating (d) up-graded film, (e) down-graded film and (f) BFO thin film; Schematic diagrams of crystal structures of BFO films (g) before and (h, i) after doping

Fig. 2 Structures and cross section morphologies of thin films (a) XRD patterns and SEM images of (b) up-graded films and (f) down-graded films. Bismuth, iron and calcium mappings of (c-e) up-graded BFO films and (g-i) down-graded BFO films

Fig. 3 Surface morphologies and domain structures of thin films (a-c) AFM images, (d-f) out-of-plane PFM images, (g-i) accordingly asymmetric phase and amplitude loops versus tip bias voltage of (a, d, g) up-graded films, (b, e, h) down-graded films and (c, f, i) BFO films

Fig. 4 J-V characteristics of thin films (a) Up-graded BFO films and down-graded BFO films; (b) BCFO (x=0, 0.05, 0.10, 0.15, 0.20) films; Colorful figures are available on website

Fig. 5 Ferroelectric properties of BFO compositionally graded films (a) Up-graded films; (b) Down-graded films; (c) BFO thin films; (d) Three kinds of films at the electric field intensity of 1500 kV/cm; (e) Remanent polarization, Pr and (f) coercive field, Ec changed with applied voltage; Colorful figures are available on website

Fig. 6 Valence analysis of thin films Narrow scan spectra of thin films: (a) O1s, (b) Fe2p, and (c) Ca2p of Bi1-xCaxFeO3 samples with x=0, 0.05, 0.10, 0.15 and 0.20; (d) Ratio of Fe3+/Fe2+ and (e) percentage of the oxygen vacancy concentration of BFCO with the increase of x

Fig. S1 AFM images, PFM images and asymmetric phase and amplitude loops versus tip bias voltage of BCFO (x=0.05, 0.10, 0.15, 0.20) films

Fig. S2 Ferroelectric properties of Bi1-xCaxFeO3 films (a) x=0; (b) x=0.05; (c) x=0.10; (d) x=0.15; (e) x=0.20; (f) The remanent polarization Pr, the coercive field Ec measured under the electric field intensity of 1800 kV·cm-1

Fig. S3 Narrow scan spectra of Bi4f of Bi1-xCaxFeO3 samples with x=0, 0.05, 0.10, 0.15 and 0.20

Fig. S3 Mechanical displacement of (a) up-graded BFO films and (b) down-graded BFO films as a function of time under an applied sinusoidal voltage

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浓度梯度掺杂实现BiFeO₃薄膜自极化

Self-polarization Achieved by Compositionally Gradient Doping in BiFeO₃ Thin Films

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