CN107082576B - 一种HoSrMnNi共掺铁酸铋多铁薄膜及其制备方法 - Google Patents

一种HoSrMnNi共掺铁酸铋多铁薄膜及其制备方法 Download PDF

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CN107082576B
CN107082576B CN201710253947.7A CN201710253947A CN107082576B CN 107082576 B CN107082576 B CN 107082576B CN 201710253947 A CN201710253947 A CN 201710253947A CN 107082576 B CN107082576 B CN 107082576B
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bismuth ferrite
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谈国强
郭美佑
杨玮
刘云
任慧君
夏傲
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Shaanxi University of Science and Technology
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Abstract

本发明提供了一种HoSrMnNi共掺铁酸铋多铁薄膜及其制备方法，以硝酸铋、硝酸钬、硝酸锶、硝酸铁、醋酸锰和乙酸镍为原料(硝酸铋过量5％)，以乙二醇甲醚和乙酸酐为溶剂，用旋涂法和层层退火的工艺制备了Bi0.89Ho0.08Sr0.03Fe0.97‑xMn0.03NixO3多铁薄膜，即HoSrMnNi共掺铁酸铋多铁薄膜。本发明采用溶胶凝胶工艺，并采用旋涂和层层退火法，设备要求简单，实验条件易于实现，适宜在大的表面和形状不规则的表面上制备薄膜，且化学组分精确可控，制得的HoSrMnNi共掺铁酸铋多铁薄膜均匀性较好，改善了BiFeO3薄膜的多铁性能。

Description

一种HoSrMnNi共掺铁酸铋多铁薄膜及其制备方法
技术领域
本发明属于功能材料领域，涉及在功能化的FTO/glass基板表面制备HoSrMnNi共掺铁酸铋多铁薄膜，具体为Bi0.89Ho0.08Sr0.03Fe0.97-xMn0.03NixO3多铁薄膜，x＝0.01～0.04。
背景技术
多铁材料是指在一定温度范围内同时具有铁电性、铁磁性和铁弹性中两种或两种以上性能的材料。在众多多铁材料中，铁酸铋(BiFeO3)是一种铁电居里温度(TC＝1103K)和反铁磁有序温度(奈尔温度，TN＝643K)都在室温以上的单相多铁性材料，BiFeO3铁电性和铁磁性的共存使得BiFeO3在磁电存储、自旋电子学等领域有潜在的应用，因此BiFeO3受到广泛的关注和研究。然而BiFeO3薄膜中铋元素的易挥发以及部分Fe3+向Fe2+的转变，使薄膜中产生较多的氧空位，从而导致其漏电流较大，难以极化，很难获得较高的剩余极化值，因此在实际应用中受到限制。为改善BiFeO3薄膜的多铁性能，最为常见的办法就是离子掺杂。目前，还没有关于Bi0.89Ho0.08Sr0.03Fe0.97-xMn0.03NixO3多铁薄膜及其制备方法的相关报道。
发明内容
本发明的目的在于提供一种HoSrMnNi共掺铁酸铋多铁薄膜及其制备方法，该方法设备要求简单，实验条件容易达到，掺杂量容易控制，制得的HoSrMnNi共掺铁酸铋多铁薄膜为Bi0.89Ho0.08Sr0.03Fe0.97-xMn0.03NixO3多铁薄膜，可改善BiFeO3基薄膜的多铁性能。
为了实现上述目的，本发明采用如下技术方案：
一种HoSrMnNi共掺铁酸铋多铁薄膜，所述HoSrMnNi共掺铁酸铋多铁薄膜为Bi0.89Ho0.08Sr0.03Fe0.97-xMn0.03NixO3薄膜，x＝0.01～0.04，该薄膜为扭曲的菱方钙钛矿结构，空间群为三方相的R3m:R和R3c:H共存。
所述HoSrMnNi共掺铁酸铋多铁薄膜在1kHz频率下，1080kV/cm测试电场下的剩余极化强度为193μC/cm2，矫顽场为335kV/cm。
所述HoSrMnNi共掺铁酸铋多铁薄膜在室温下的饱和磁化强度为5.78emu/cm3，剩余磁化强度0.52emu/cm3，磁矫顽场为50Oe。
所述的HoSrMnNi共掺铁酸铋多铁薄膜的制备方法，包括以下步骤：
步骤1：按摩尔比为0.94:0.08:0.03:(0.97-x):0.03:x将硝酸铋、硝酸钬、硝酸锶、硝酸铁、醋酸锰和乙酸镍溶于乙二醇甲醚中，搅拌均匀后加入醋酸酐，继续搅拌均匀，得到前驱液；其中x＝0.01～0.04；
步骤2：将前驱液旋涂在FTO/glass基片上，得到湿膜，湿膜经匀胶后在190～220℃下烘烤得干膜，再于540～560℃下在空气中退火，得到晶态Bi0.89Ho0.08Sr0.03Fe0.97- xMn0.03NixO3薄膜；
步骤3：将晶态Bi0.89Ho0.08Sr0.03Fe0.97-xMn0.03NixO3薄膜冷却至室温，重复步骤2直到达到所需厚度，即得到HoSrMnNi共掺铁酸铋多铁薄膜。
所述步骤1中前驱液中金属离子的总浓度为0.2～0.4mol/L。
所述前驱液中乙二醇甲醚和醋酸酐的体积比为(2.5～3.5):1。
所述步骤2进行前先将FTO/glass基片清洗干净，然后在紫外光下照射，使FTO/glass基片表面达到原子清洁度。
所述步骤2中匀胶时的匀胶转速为3800～4000r/min，匀胶时间为12～18s。
所述步骤2中匀胶后的烘烤时间为8～10min。
所述步骤2中的退火时间为20～25min。
相对于现有技术，本发明具有以下有益效果：
本发明提供的HoSrMnNi共掺铁酸铋多铁薄膜的制备方法，采用溶胶-凝胶法，以硝酸铋、硝酸钬、硝酸锶、硝酸铁、醋酸锰和乙酸镍为原料(硝酸铋过量5％)，以乙二醇甲醚和乙酸酐为溶剂，配制前驱液，再用旋涂法和层层退火的工艺制备了Bi0.89Ho0.08Sr0.03Fe0.97- xMn0.03NixO3薄膜，即HoSrMnNi共掺铁酸铋多铁薄膜。本发明选择碱土元素Sr和镧系元素Ho进行A位掺杂，选择过渡金属Mn和Ni进行B位掺杂，使原本近似呈钙钛矿结构的铁酸铋晶格扭曲，结构畸变加剧，同时由于Sr和Ho对Bi3+的替代，以及Mn和Ni元素在退火过程中的变价，可以有效的拟制Bi的挥发，减少薄膜中Fe2+和氧空位的含量，结构进一步发生畸变，从而增强薄膜在外加电场下的极化强度。此外，这种结构的畸变会抑制BFO特殊的空间调制的螺旋磁结构，释放出部分潜在的宏观磁性，提高薄膜的铁磁性。本发明采用溶胶-凝胶工艺，相比于其他制备薄膜的方法，该方法设备要求简单，实验条件易于实现，成本低廉，反应容易进行，工艺过程温度低，制备过程及掺杂量容易控制，化学组分精确可控，适宜在大的表面和形状不规则的表面上制备薄膜，很容易均匀定量地掺入一些微量元素，可以在短时间内获得原子或分子水平的均匀性，本发明制备的HoSrMnNi共掺铁酸铋多铁薄膜均匀性较好，具有随外加电压变化的铁电稳定性。
本发明制得的HoSrMnNi共掺铁酸铋多铁薄膜的致密度高、晶粒尺寸均匀，其化学结构式为Bi0.89Ho0.08Sr0.03Fe0.97-xMn0.03NixO3，x＝0.01～0.04，该薄膜为扭曲的菱方钙钛矿结构，空间群为三方相的R3m:R和R3c:H共存，本发明通过Sr、Ho、Mn和Ni四元共掺杂BiFeO3薄膜，显著的提高了剩余极化值，减小了矫顽场，同时也增强了饱和磁化强度，能够改善BiFeO3基薄膜的多铁性能，有利于BiFeO3薄膜在磁电耦合方面的应用。
进一步的，本发明制得的HoSrMnNi共掺铁酸铋多铁薄膜在1kHz频率下，1080kV/cm测试电场下的剩余极化强度为193μC/cm2，矫顽场为335kV/cm。本发明制得的HoSrMnNi共掺铁酸铋多铁薄膜在室温下的饱和磁化强度为5.78emu/cm3，剩余磁化强度0.52emu/cm3。
附图说明
图1是本发明实施例2制备的HoSrMnNi共掺铁酸铋多铁薄膜的XRD图；
图2是本发明实施例2制备的HoSrMnNi共掺铁酸铋多铁薄膜的SEM图；
图3是本发明实施例2制备的HoSrMnNi共掺铁酸铋多铁薄膜的SEM断面图；
图4是本发明实施例2制备的HoSrMnNi共掺铁酸铋多铁薄膜的电滞回线图；
图5是本发明实施例2制备的HoSrMnNi共掺铁酸铋多铁薄膜的磁滞回线图。
具体实施方式
下面结合附图和本发明优选的具体实施例对本发明做进一步描述，原料均为分析纯。
实施例1
步骤1：以硝酸铋、硝酸钬、硝酸锶、硝酸铁、醋酸锰和乙酸镍为原料(硝酸铋过量5％)，按摩尔比为0.94:0.08:0.03:0.96:0.03:0.01(x＝0.01)溶于乙二醇甲醚中，搅拌30min，再加入醋酸酐，搅拌90min，得到金属离子总浓度为0.2mol/L的稳定的前驱液；其中乙二醇甲醚和醋酸酐的体积比为2.5:1；
步骤2：将FTO/glass基片依次置于洗涤剂、丙酮、乙醇中超声波清洗，每次超声波清洗10min后用大量蒸馏水冲洗基片，最后用氮气吹干。然后将FTO/glass基片放入烘箱烘烤至干燥，取出静置至室温。再将洁净的基片置于紫外光照射仪中照射40min，使基片表面达到“原子清洁度”。然后将前驱液旋涂在FTO/glass基片上，其匀胶转速为4000r/min，匀胶时间为12s，得到湿膜，湿膜在210℃下烘烤8min得干膜，再在555℃下在空气中退火20min，即得晶态Bi0.89Ho0.08Sr0.03Fe0.96Mn0.03Ni0.01O3薄膜；
步骤3：将晶态Bi0.89Ho0.08Sr0.03Fe0.96Mn0.03Ni0.01O3薄膜冷却至室温，重复步骤2，重复13次，即得到HoSrMnNi共掺铁酸铋多铁薄膜。
实施例2
步骤1：以硝酸铋、硝酸钬、硝酸锶、硝酸铁、醋酸锰和乙酸镍为原料(硝酸铋过量5％)，按摩尔比为0.94:0.08:0.03:0.95:0.03:0.02(x＝0.02)溶于乙二醇甲醚中，搅拌30min，再加入醋酸酐，搅拌90min，得到金属离子总浓度为0.3mol/L的稳定的前驱液；其中乙二醇甲醚和醋酸酐的体积比为3:1；
步骤2：将FTO/glass基片依次置于洗涤剂、丙酮、乙醇中超声波清洗，每次超声波清洗10min后用大量蒸馏水冲洗基片，最后用氮气吹干。然后将FTO/glass基片放入烘箱烘烤至干燥，取出静置至室温。再将洁净的基片置于紫外光照射仪中照射40min，使基片表面达到“原子清洁度”。然后将前驱液旋涂在FTO/glass基片上，其匀胶转速为3900r/min，匀胶时间为15s，得到湿膜，湿膜在200℃下烘烤9min得干膜，再在550℃下在空气中退火23min，即得晶态Bi0.89Ho0.08Sr0.03Fe0.95Mn0.03Ni0.02O3薄膜；
步骤3：将晶态Bi0.89Ho0.08Sr0.03Fe0.95Mn0.03Ni0.02O3薄膜冷却至室温，重复步骤2，重复12次，即得到HoSrMnNi共掺铁酸铋多铁薄膜。
采用X-射线衍射仪测定HoSrMnNi共掺铁酸铋多铁薄膜的物相组成结构；用FE-SEM测定HoSrMnNi共掺铁酸铋多铁薄膜的微观形貌；用Radiant Multiferroic仪器测试HoSrMnNi共掺铁酸铋多铁薄膜的漏电流密度和铁电性能，用SQUID MPMS-XL-7测试HoSrMnNi共掺铁酸铋多铁薄膜室温下的铁磁性能。
对实施例2制得的HoSrMnNi共掺铁酸铋多铁薄膜进行以上测试，结果如图1、图2、图3、图4和图5所示。
图1与JCPDS No.74-2016标准卡片吻合，从图1中可知，实施例2制得的HoSrMnNi共掺铁酸铋多铁薄膜具有扭曲的菱方钙钛矿结构，空间群为三方相的R3m:R和R3c:H共存，薄膜结晶性能良好，薄膜样品中没有其他杂质的出现。
图2表明实施例2制得的HoSrMnNi共掺铁酸铋多铁薄膜结构致密，晶粒尺寸分布均匀，晶粒发育良好。
图3表明实施例2制得的HoSrMnNi共掺铁酸铋多铁薄膜的厚度是410nm。
图4表明实施例2制得的HoSrMnNi共掺铁酸铋多铁薄膜在1kHz频率下，1080kV/cm测试电场下的剩余极化强度为193μC/cm2，矫顽场为335kV/cm。
图5表明实施例2制得的HoSrMnNi共掺铁酸铋多铁薄膜室温下的饱和磁化强度为5.78emu/cm3，剩余磁化强度0.52emu/cm3，磁矫顽场为50Oe。
实施例3
步骤1：以硝酸铋、硝酸钬、硝酸锶、硝酸铁、醋酸锰和乙酸镍为原料(硝酸铋过量5％)，按摩尔比为0.94:0.08:0.03:0.94:0.03:0.03(x＝0.03)溶于乙二醇甲醚中，搅拌30min，再加入醋酸酐，搅拌90min，得到金属离子总浓度为0.4mol/L的稳定的前驱液；其中乙二醇甲醚和醋酸酐的体积比为3.5:1；
步骤2：将FTO/glass基片依次置于洗涤剂、丙酮、乙醇中超声波清洗，每次超声波清洗10min后用大量蒸馏水冲洗基片，最后用氮气吹干。然后将FTO/glass基片放入烘箱烘烤至干燥，取出静置至室温。再将洁净的基片置于紫外光照射仪中照射40min，使基片表面达到“原子清洁度”。然后将前驱液旋涂在FTO/glass基片上，其匀胶转速为3800r/min，匀胶时间为18s，得到湿膜，湿膜在190℃下烘烤10min得干膜，再在540℃下在空气中退火25min，即得晶态Bi0.89Ho0.08Sr0.03Fe0.94Mn0.03Ni0.03O3薄膜；
步骤3：将晶态Bi0.89Ho0.08Sr0.03Fe0.94Mn0.03Ni0.03O3薄膜冷却至室温，重复步骤2，重复11次，即得到HoSrMnNi共掺铁酸铋多铁薄膜。
实施例4
步骤1：以硝酸铋、硝酸钬、硝酸锶、硝酸铁、醋酸锰和乙酸镍为原料(硝酸铋过量5％)，按摩尔比为0.94:0.08:0.03:0.93:0.03:0.04(x＝0.04)溶于乙二醇甲醚中，搅拌30min，再加入醋酸酐，搅拌90min，得到金属离子总浓度为0.32mol/L的稳定的前驱液；其中乙二醇甲醚和醋酸酐的体积比为3.2:1；
步骤2：将FTO/glass基片依次置于洗涤剂、丙酮、乙醇中超声波清洗，每次超声波清洗10min后用大量蒸馏水冲洗基片，最后用氮气吹干。然后将FTO/glass基片放入烘箱烘烤至干燥，取出静置至室温。再将洁净的基片置于紫外光照射仪中照射40min，使基片表面达到“原子清洁度”。然后将前驱液旋涂在FTO/glass基片上，其匀胶转速为4000r/min，匀胶时间为14s，得到湿膜，湿膜在220℃下烘烤8.5min得干膜，再在560℃下在空气中退火22min，即得晶态Bi0.89Ho0.08Sr0.03Fe0.93Mn0.03Ni0.04O3薄膜；
步骤3：将晶态Bi0.89Ho0.08Sr0.03Fe0.93Mn0.03Ni0.04O3薄膜冷却至室温，重复步骤2，重复12次，即得到HoSrMnNi共掺铁酸铋多铁薄膜。
以上所述内容是结合具体的优选实施方式对本发明所作的进一步详细说明，不是全部或唯一的实施方式，本领域普通技术人员通过阅读本发明说明书而对本发明技术方案采取的任何等效的变换，均为本发明的权利要求所涵盖。

Claims (6)

1.一种HoSrMnNi共掺铁酸铋多铁薄膜，其特征在于，所述HoSrMnNi共掺铁酸铋多铁薄膜为Bi0.89Ho0.08Sr0.03Fe0.97-xMn0.03NixO3薄膜，x＝0.01～0.04，该薄膜为扭曲的菱方钙钛矿结构，空间群为三方相的R3m:R和R3c:H共存；所述HoSrMnNi共掺铁酸铋多铁薄膜在1kHz频率下，1080kV/cm测试电场下的剩余极化强度为193μC/cm2，矫顽场为335kV/cm；所述HoSrMnNi共掺铁酸铋多铁薄膜在室温下的饱和磁化强度为5.78emu/cm3，剩余磁化强度0.52emu/cm3，磁矫顽场为50Oe。
2.权利要求1中任意一项所述的HoSrMnNi共掺铁酸铋多铁薄膜的制备方法，其特征在于，包括以下步骤：
步骤1：按摩尔比为0.94:0.08:0.03:(0.97-x):0.03:x将硝酸铋、硝酸钬、硝酸锶、硝酸铁、醋酸锰和乙酸镍溶于乙二醇甲醚中，搅拌均匀后加入醋酸酐，继续搅拌均匀，得到前驱液；其中x＝0.01～0.04；
步骤2：将前驱液旋涂在FTO/glass基片上，得到湿膜，湿膜经匀胶后在190～220℃下烘烤得干膜，再于540～560℃下在空气中退火，得到晶态Bi0.89Ho0.08Sr0.03Fe0.97-xMn0.03NixO3薄膜；
步骤3：将晶态Bi0.89Ho0.08Sr0.03Fe0.97-xMn0.03NixO3薄膜冷却至室温，重复步骤2直到达到所需厚度，即得到HoSrMnNi共掺铁酸铋多铁薄膜；
所述步骤2中匀胶后的烘烤时间为8～10min；
所述步骤2中的退火时间为20～25min。
3.根据权利要求2所述的HoSrMnNi共掺铁酸铋多铁薄膜的制备方法，其特征在于，所述步骤1中前驱液中金属离子的总浓度为0.2～0.4mol/L。
4.根据权利要求2所述的HoSrMnNi共掺铁酸铋多铁薄膜的制备方法，其特征在于，所述前驱液中乙二醇甲醚和醋酸酐的体积比为(2.5～3.5):1。
5.根据权利要求2所述的HoSrMnNi共掺铁酸铋多铁薄膜的制备方法，其特征在于，所述步骤2进行前先将FTO/glass基片清洗干净，然后在紫外光下照射，使FTO/glass基片表面达到原子清洁度。
6.根据权利要求2所述的HoSrMnNi共掺铁酸铋多铁薄膜的制备方法，其特征在于，所述步骤2中匀胶时的匀胶转速为3800～4000r/min，匀胶时间为12～18s。
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