铁电极化诱导的<strong>PbTiO<sub>3</sub></strong>薄膜的取向聚集生长和晶粒尺寸调控

doi:10.11901/1005.3093.2020.150

材料研究学报

2020, Vol. 34

Issue (9): 650-658 DOI: 10.11901/1005.3093.2020.150

研究论文

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铁电极化诱导的PbTiO₃薄膜的取向聚集生长和晶粒尺寸调控

武梦姣¹, 任召辉¹(

), 田鹤², 韩高荣¹

1.浙江大学材料科学与工程学院硅材料国家重点实验室杭州 310027
2.浙江大学材料科学与工程学院电子显微镜中心杭州 310027

Ferroelectric Polarization Induced Oriented Attachment Growth of PbTiO₃ Films and Grain Size Control

WU Mengjiao¹, REN Zhaohui¹(

), TIAN He², HAN Gaorong¹

1. State Key Laboratory of Silicon Materials, School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China
2. Center of Electron Microscope, School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China

引用本文:

武梦姣, 任召辉, 田鹤, 韩高荣. 铁电极化诱导的PbTiO₃薄膜的取向聚集生长和晶粒尺寸调控[J]. 材料研究学报, 2020, 34(9): 650-658.
Mengjiao WU, Zhaohui REN, He TIAN, Gaorong HAN. Ferroelectric Polarization Induced Oriented Attachment Growth of PbTiO₃ Films and Grain Size Control[J]. Chinese Journal of Materials Research, 2020, 34(9): 650-658.

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摘要:

用溶胶凝胶法制备了PbTiO₃薄膜。将含量为0.2%、0.5%和0.8%(摩尔比)的钙钛矿铁电PbTiO₃纳米片加入溶胶体系中，利用纳米片的自发极化调控薄膜的生长。结果表明，纳米片的加入显著影响了薄膜的生长过程和结晶学取向，可制备出(100)高度取向的PbTiO₃薄膜；改变纳米片的浓度，可将薄膜晶粒尺寸由100 nm调控到2 μm。扫描电子显微镜(SEM)、透射电子显微镜(TEM)观测和原位X射线衍射(in-situ XRD)的结果表明，固态薄膜中的晶粒表现出类液相的取向聚集生长特征。其原因可能是，铁电纳米片极化表面的静电力诱导小晶粒的吸附和取向排列，调控了薄膜的(100)取向和晶粒尺寸。

关键词 ：无机非金属材料, 钛酸铅, 溶胶凝胶法, 铁电极化, 取向聚集生长

Abstract：

PbTiO₃ (PTO) ferroelectric thin films were synthesized by a sol-gel process, where different concentration (0.2%, 0.5%, 0.8%, mole ratio) of PbTiO₃ nanoplates with large spontaneous polarity were introduced to the sol system to manipulate the growth and microstructures of PbTiO₃ films. The products were then characterized by means of X-ray diffractometer(XRD), scanning electron microscope (SEM), transmission electron microscope (TEM). The effect of PTO nanoplates on the growth mechanism of PTO films was investigated by in-situ XRD. It was found that nanoplates dramatically affected the growth process and crystallographic orientation of PbTiO₃ films, giving rise to a preferred orientation of (100) in PbTiO₃ films. In addition, an effective control of grain size of PbTiO₃ films ranging from 100 nm to 2 μm has been realized by altering the concentration of nanoplates. According to results of SEM, TEM and in-situ XRD analysis, the grains in solid-state films exhibited the growth characteristics of orientation related gathering of gains, similar to that in liquid phase. This growth behavior can be attributed to the strong electrostatic force originated from polar surfaces of nanoplates, which induced the adsorption and oriented alignment of small grains, accounting for the orientation and grain size evolution.

Key words： inorganic non-metallic materials lead titanate sol-gel method ferroelectric polarization oriented attachment growth

收稿日期: 2020-05-03

ZTFLH:

TB34

基金资助:国家自然科学基金(U1909212);浙江省重点研发计划(2020C01124);中央高校基本科研业务费(2020FZZX002);中央高校基本科研业务费(2020-FZZX003)

作者简介: 武梦姣，女，1993年生，博士生

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https://www.cjmr.org/CN/10.11901/1005.3093.2020.150 或 https://www.cjmr.org/CN/Y2020/V34/I9/650

图1 纳米片的SEM照片、DTA和TGA曲线和横截面的ABF-STEM图

图2 添加不同含量纳米片制备的PTO薄膜的XRD图谱及其图中19-35o部分的放大图和(100)取向比例与纳米片含量的关系

图3 添加不同含量纳米片的PTO薄膜的SEM照片

图4 添加0.5%纳米片的PTO薄膜的断面TEM照片及其PTO薄膜的选取电子衍射图(SAED)、两个晶粒晶界区域的TEM照片及其方框区域的高倍TEM照片

图5 添加0.5%纳米片的PTO前驱体干燥凝胶粉末的DTA和TGA曲线

图6 添加0.5%纳米片的PTO前驱体干燥凝胶粉末在不同温度热处理后的FTIR图

图7 PTO前驱体凝胶膜的原位XRD图谱

图8 PTO薄膜中纳米片区域的SEM照片、PTO薄膜取向聚集生长四个过程的示意图以及OA生长的最终形貌

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