硅酸盐学报

锰掺杂诱导层状类钙钛矿结构薄膜取向生长及铁电性能

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惠贞贞 ¹ , 宋怡瑶 ¹ , 宋东坡 ²^,³

硅酸盐学报 | 研究论文 2026,54(6): 1973-1979

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硅酸盐学报 |研究论文 2026 , 54 (6) : 1973 -1979

锰掺杂诱导层状类钙钛矿结构薄膜取向生长及铁电性能

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惠贞贞¹, 宋怡瑶¹, 宋东坡²^,³

作者信息

^1．安徽科技学院化学与材料工程学院，安徽凤阳 233100

^2．江苏科技大学理学院，江苏镇江 212003

^3．安徽省硅基新材料特色产业创新研究院，安徽凤阳 233100

通讯作者:

宋东坡（1986—），男，博士，副教授。

作者简介:

惠贞贞（1988—），女，博士，副教授。

Mn-Doped Induced Orientation and Ferroelectric Properties in Layered Perovskite-Like Structure Thin Films

Zhenzhen HUI¹, Yiyao SONG¹, Dongpo SONG²^,³

Affiliations

^1.College of Chemistry and Materials Engineering, Anhui Science and Technology University, Fengyang 233100, Anhui, China

^2.Department of Physics, Jiangsu University of Science and Technology, Zhenjiang 212003, Jiangsu, China

^3.Anhui Province Silicon-based New Materials Characteristic Industry Innovation Research Institute, Fengyang 233100, Anhui, China

Corresponding Author:

{SONG} Dongpo (1986-), male, Ph.D., Associate Professor. E-mail: dpsong@just.edu.cn

HUI Zhenzhen (1988-), female, Ph.D., Associate Professor. E-mail: huizz@ahstu.edu.cn

出版时间: 2026-05-12 doi: 10.14062/j.issn.0454-5648.20250934

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摘要

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以5层Aurivillius化合物为研究对象，采用化学溶液沉积法制备锰掺杂的Bi₇Fe_3-_xMn_xTi₃O₂₁薄膜，系统研究了锰掺杂对薄膜晶体生长及铁电极化的影响。结果表明，Mn³⁺掺杂可显著诱导层状类钙钛矿薄膜的c轴择优取向生长，取向因子提升10倍。表明该现象源于锰离子掺杂降低了薄膜晶化温度以及c面界面能较低的协同作用。薄膜铁电性能随掺杂量的增加呈现先升后降的趋势，在x=0.50时有效剩余极化达到峰值。低掺杂浓度下的剩余极化均高于母体材料，此阶段晶粒尺寸为极化增强的主导因素。相比之下，在高掺杂浓度下，铁电性能急剧恶化，这主要归因于薄膜质量的下降和持续的取向增长，研究为Aurivillius型层状钙钛矿薄膜的取向生长与铁电性能调控提供了可靠的实验依据，不仅印证了该类薄膜铁电极化的结构各向异性特征，更为择优取向薄膜的可控制备与性能优化提供了切实可行的技术途径。

关键词

化学溶液沉积法 / Aurivillius / 铁电性能 / 择优取向

Abstract

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Introduction

The Aurivillius type layered perovskite structure compound can be represented by a chemical formula (Bi₂O₂)²⁺(A_n_-1B_nO₃_n₊₁)^2-. Its crystal structure can be seen as a unique "natural superlattice" structure composed of alternating layers of perovskite-like structure and fluorite-like structure along the c-axis direction. Among them, n represents the number of layers of BO₆ octahedra in the c-axis direction in the perovskite structure layer (i.e., n = 1, 2, 3, 4, 5, ...). The value of n determines the thickness of the perovskite layer and physical properties of the material. The A-site ion is located at the octahedral apex of the perovskite like layer, with 12 coordination. Usually, it can be larger cations such as Ba²⁺, Sr²⁺, Ca²⁺, Pb²⁺, K¹⁺, Na¹⁺, Bi³⁺, and Ln³⁺(lanthanide elements). Multiple ion substitutions can be achieved to regulate the performance. The B-site ion is located at the center of the oxygen octahedron and coordinated with 6. Usually, it can be small high valence transition metal ions such as Fe³⁺, Ti⁴⁺, Nb⁵⁺, Ta⁵⁺, W⁶⁺, and Mo⁶⁺). The displacement of B-site ions is one of the main sources of ferroelectric polarization. The stereochemical activity of the 6s² lone pair electrons of Bi³⁺ ions also has a significant impact on their structure and polarization. From the chemical formula and crystal structure above, it can be inferred that this type of compound can have a broad spectrum of physical and chemical properties as well as tunability, while the physical and chemical properties can be accompanied by significant anisotropic characteristics.

Methods

Acetate and tetrabutyl titanate [Ti(OC₄H₉)₄] were used as starting materials solvent in acidic solutions. A 10% excess amount of Bi(CH₃COO)₃ was used to compensate the Bi volatilization in the process. Before spin coating, the substrates were cleaned ultrasonically in acetone, alcohol and deionized water, sequently. The spin coating and baking processing were repeated to enhance the thickness. Finally, the baked thin films were crystallized in ambient atmosphere at 700 ℃ for 10 min by rapid thermal annealing.

The crystal structure for the derived thin films was determined by X-ray diffraction (XRD, Philips Co., the Netherlands) with Cu k_α radiation. The thickness and the surface morphologies were characterized by field-emission scanning electron microscopy (FE-SEM, FEI Co., Japan). Au electrodes of 0.2 mm in diameter were deposited by a sputter (China) onto the surfaces of thin films through a shadow mask. The ferroelectric and leakage properties were measured by a standard ferroelectric test system (Radiant Technologies Co., USA).

Results and discussion

For the sample with x of 0, its main diffraction peaks correspond one-to-one with the six-layered perovskite structure, which can be classified as the A2₁am space group, belonging to a typical even layered Aurivillius type compound. There are no diffraction peaks of other impurities except for the substrate diffraction peak. After introducing element Mn doping, the doped film still maintains the layered structure characteristic peak position as a whole, and there is no significant shift. In general, doping often leads to a shift in diffraction peak position due to the difference in ionic radius, which is usually one of the reference evidences for doping elements entering the main lattice. There is no significant shift in the diffraction peak position of the Mn ion doped film possibly due to the unsuccessful entry of Mn ions into the main lattice or the fact that the radius of Mn ion (0.064 5 nm) is the same as the radius of Fe ion (0.064 5 nm). As x increases, the most intense diffraction peak of the sample gradually shifts from (1113) to (0014), and the (00l) series diffraction peaks gradually increase in intensity, indicating that the c-axis orientation of the thin film is strengthened. This change is not significant in ceramic samples, but it is also evident. The change in relative peak intensity also confirms the doping of Mn ions into the main lattice, indicating that the diffraction peak position is not significantly shifted due to the same ion radius. For the structural characteristics of Aurivillius type compounds, especially their polarization anisotropy, this preferred orientation can inevitably have a profound impact on the electrical properties of thin films.

Conclusions

The BFTM thin films doped with manganese ions were prepared by a chemical solution method. The preferred orientation of the film's c-axis enhanced, and the orientation factor increased from 0.08 as x=0 to 0.89 as x=1.00 with the increase of manganese ion doping content. The ferroelectric properties of the thin film were enhanced with doping, and the effective residual polarization reached its maximum as x=0.50. This work could provide an experimental reference for the preparation and ferroelectric properties of Aurivillius type layered perovskite structure thin films. These results could indicate the anisotropic characteristics of the crystal structure polarization of this type of compound, and provide feasible strategies for the preparation of preferred orientation thin films and performance control.

Key words

chemical solution deposition method / Aurivillius / ferroelectric properties / preferred orientat

引用本文

惠贞贞, 宋怡瑶, 宋东坡. 锰掺杂诱导层状类钙钛矿结构薄膜取向生长及铁电性能. 硅酸盐学报, 2026 , 54 (6) : 1973 -1979 . DOI: 10.14062/j.issn.0454-5648.20250934

Zhenzhen HUI, Yiyao SONG, Dongpo SONG. Mn-Doped Induced Orientation and Ferroelectric Properties in Layered Perovskite-Like Structure Thin Films[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (6) : 1973 -1979 . DOI: 10.14062/j.issn.0454-5648.20250934

基金

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国家自然科学基金(12104188)
安徽省青年皖江学者计划(830523)
安徽省硅基新材料特色产业创新研究院开放基金(GYKF250107)
安徽省应用型高峰培育学科项目(XK-XJGF005)

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2026年第54卷第6期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250934

接收时间：2025-12-26
首发时间：2026-10-22
出版时间：2026-05-12

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收稿日期：2025-12-26
修回日期：2026-01-30

基金

国家自然科学基金(12104188)

安徽省青年皖江学者计划(830523)

安徽省硅基新材料特色产业创新研究院开放基金(GYKF250107)

安徽省应用型高峰培育学科项目(XK-XJGF005)

作者信息

^1．安徽科技学院化学与材料工程学院，安徽凤阳 233100

^2．江苏科技大学理学院，江苏镇江 212003

^3．安徽省硅基新材料特色产业创新研究院，安徽凤阳 233100

通讯作者:

宋东坡（1986—），男，博士，副教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250934

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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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