CN114107913A - 一种高熵钙钛矿氧化物薄膜材料及其制备方法 - Google Patents
一种高熵钙钛矿氧化物薄膜材料及其制备方法 Download PDFInfo
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Abstract
本发明属于材料制备技术领域,具体涉及一种高熵钙钛矿氧化物薄膜材料及其制备方法。本发明首先制备得到一种新型的磁性材料为La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3(L5BO),其借助各序参量之间的耦合效应有潜力实现更为丰富、新颖的物理特征;然后,以L5BO高熵金属氧化物陶瓷靶材,借助脉冲激光沉积技术在SrTiO3(STO)单晶衬底上生长L5BO薄膜。本发明得到质量良好的单晶高熵钙钛矿型氧化物外延薄膜。本发明首次在单晶纯相的氧化物外延薄膜中实现磁滞回线在垂直方向的位移调控,在磁性器件中有巨大的应用潜力。
Description
技术领域
本发明属于材料制备技术领域,具体涉及一种高熵钙钛矿氧化物薄膜材料及其制备方法。
背景技术
钙钛矿氧化物薄膜材料由于具有丰富的物理内涵及广泛的应用场景,长久以来吸引了大量研究人员的关注。基于钙钛矿氧化物薄膜材料的自旋阀、磁隧道结等一系列器件构成了现代众多电子设备的基础,因此优化现有的材料性能和开发新的材料体系对于拓展钙钛矿氧化物薄膜材料的应用、推动电子设备的迭代更新有重要意义。调控钙钛矿氧化物薄膜材料性能的常见手段主要有应变调控、改变薄膜生长气氛以及元素掺杂等。其中应变调控是通过选择合适的衬底对外延生长的钙钛矿氧化物薄膜施加外延应力,驱动晶体场分裂,改变磁性离子自旋状态,从而调控磁性能;改变薄膜生长气氛是指调节薄膜外延生长过程中的背景气体的种类及压强大小,从而改变薄膜中离子的价态、载流子浓度,进而调控薄膜的磁性;元素掺杂是指在钙钛矿氧化物基体材料中掺杂引入其它元素,根据需求选择掺杂元素的种类及比例,如掺入磁性元素或者施主受主元素,从而改变离子的磁耦合结构。
调控钙钛矿氧化物薄膜材料的现有手段中应变调控通常需要特定的衬底来提供合适的应力,因此对于不同的钙钛矿氧化物薄膜材料需要借助不同的衬底,并且随着薄膜厚度变化应变状态也会随之改变;改变薄膜生长气氛对于不同的材料可能需要不同种类的背景气体甚至混合气体,此外改变生长气氛可能会同时改变薄膜的外延生长质量,导致表面粗糙度或者结晶性恶化;元素掺杂改性的方法操作简单,但掺杂比例过大容易导致第二相析出,反而使得材料性能恶化,因此目前大多采用单一元素以小比例掺杂。总体而言上述方法改性效果有限。
发明内容
鉴于现有技术存在的问题,本发明开发新的方法来制备一种高熵钙钛矿氧化物薄膜材料,具有良好的外延生长性和新颖的磁性特征,在磁性器件的开发上有巨大的应用潜力。
本发明选择了ABO3型钙钛矿氧化物磁性材料为基体材料,这是由于它们具备外延生长性良好、磁性较强等优点,且大部分ABO3型钙钛矿氧化物属于强关联电子体系,其具有本征的自旋、电荷、晶格、轨道序参量的耦合,即只要其中一种序参量发生变化,其他序参量都会产生非线性的相应变化,有利于实现新颖的磁性特征。在基体材料中以等摩尔比掺杂混合多种磁性过渡金属元素,使得占据B位的金属元素种类达到5种或5种以上,此时会产生较大的混合熵,促使相同的热力学温度下混合后系统的吉布斯自由能较低,从而能够以单相的形式稳定存在。多种磁性过渡金属元素的引入可以保证基体材料具有足够的磁性。高熵的引入会显著提高体系的无序度,并调控其本征的序参量,借助各序参量之间的耦合,可以很大程度地提高高熵ABO3型钙钛矿氧化物出现奇异物理性能的可能性。
本发明首先采用固相反应法合成制备得到一种新型的磁性材料为La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3(L5BO)。然后,以L5BO高熵金属氧化物陶瓷靶材,借助脉冲激光沉积技术在SrTiO3(STO)单晶衬底上生长44~48nm厚度的L5BO薄膜。
本发明通过以下技术方案来实现,包括:
本发明首先提供了一种高熵钙钛矿氧化物薄膜材料的制备方法,包括:
步骤S1,制备多晶La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3靶材:将La2O3、NiO、MnO2、Fe2O3、Co3O4和Cr2O3粉末混合,烧结后得到La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3靶材;
步骤S2,薄膜制备:采用La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3靶材,通过脉冲激光沉积的方法在衬底上进行薄膜沉积,得到高熵钙钛矿氧化物薄膜材料。
采用此技术方案,借助脉冲激光沉积技术在不同结构的单晶衬底上均可实现对应成分薄膜的高质量外延生长。
作为本发明的进一步改进,步骤S1中,将La2O3、NiO、MnO2、Fe2O3、Co3O4和Cr2O3按照摩尔比混合均匀,通过烧结得到La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3陶瓷靶材。采用此技术方案,在ABO3型钙钛矿基体材料中,以等摩尔比掺杂混合多种磁性过渡金属元素替代B位原子,使得B位元素的种类达到5种或5种以上,在沉积薄膜的过程中,不容易产生第二相析出,提高了高熵单相的稳定性,而且选择磁性元素混合后得到的材料具备较强的磁性。
作为本发明的进一步改进,步骤S1中La2O3、NiO、MnO2、Fe2O3、Co3O4和Cr2O3的纯度为99.99%。
作为本发明的进一步改进,步骤S2中所述脉冲激光沉积的参数为:温度600-650℃、激光能量密度为0.6-1.0J/cm2,氧压为50-150mTorr,脉冲频率为3-7Hz,沉积结束后在75Torr氧压下冷却至室温。
作为本发明的进一步改进,步骤S2中所述衬底可选择但不仅限于钙钛矿结构的LaAlO3、钙钛矿结构的SrTiO3、尖晶石结构的MgAl2O4或岩盐结构的MgO。
本发明进一步提供了一种新型的磁性材料为La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3(L5BO),通过前述制备方法获得。
本发明进一步提供了一种高熵钙钛矿氧化物薄膜材料,通过前述制备方法获得。
本发明进一步提供了一种新型的磁性材料为La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3(L5BO),通过前述制备方法获得。
本发明相对于现有技术的有益效果包括:
1.本发明选择钙钛矿型氧化物为基体材料,通过多种元素以等摩尔比掺杂,产生较大的混合熵,使得混合后系统的吉布斯自由能降低,从而能够以单相稳定存在,避免了第二相的析出,成功得到质量良好的单晶高熵钙钛矿型氧化物外延薄膜。
2.本发明首次在单晶纯相的氧化物外延薄膜中实现磁滞回线在垂直方向的位移调控,在磁性器件中有巨大的应用潜力。
3.本发明制备的高熵磁性薄膜可通过改变掺杂元素种类及含量,调控其自旋、电荷、晶格、或轨道等序参量,借助各序参量之间的耦合效应有潜力实现更为丰富、新颖的物理特征。
附图说明
以下,结合附图来详细说明本发明的实施方案,其中:
图1是本发明实施例1制备的La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3高熵钙钛矿氧化物薄膜材料的X射线衍射图谱(XRD)。
图2是本发明实施例1制备的La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3高熵钙钛矿氧化物薄膜材料的X射线反射图谱(XRR)。
图3是本发明实施例1制备的La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3高熵钙钛矿氧化物薄膜材料的高分辨透射电镜图及Cr、Mn、Fe、Co、Ni各B位元素的电子能量损失图。
图4是本发明实施例1制备的La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3高熵钙钛矿氧化物薄膜材料的Cr L2,3边、Mn L2,3边、Fe L2,3边、Co L2,3边和Ni L2,3边的X射线吸收谱(XAS)、X射线线性二色谱(XLD)和X射线磁性圆二色吸收谱(XMCD)。
图5是本发明实施例1制备的La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3高熵钙钛矿氧化物薄膜材料的磁特性。其中,图5中a为场冷却和零场冷却过程的磁化曲线,图5中b为La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3高熵钙钛矿氧化物薄膜材料的垂直交换偏置效应,图5中c为La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3/La0.67Sr0.33MnO3异质结的垂直交换偏置效应。图5中b和图5中c中的实线和虚线分别表示样品在不同方向的外加磁场中冷却的结果。
具体实施方式
下面结合具体实施方式和附图对本发明进行进一步的详细描述,给出的实施例仅为了阐明本发明,而不是为了限制本发明的范围。
实施例1
本实施例的制备方法如下:
1)将纯度为99.9%的La2O3、NiO、MnO2、Fe2O3、Co3O4和Cr2O3粉末按摩尔比15:6:6:3:2:3混合后烧结得到La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3靶材。
2)将La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3靶材置于PLD系统中的靶材位置,将SrTiO3衬底置于系统中衬底的位置;
3)对PLD腔室抽真空至1×10^-4Pa,并将衬底温度升温至625℃,调节动态氧压为100mTorr。
4)打开激光器,设置激光能量为0.82J/cm2,脉冲频率为5Hz,脉冲数为3100个。
5)打开激光挡板及加热器挡板,制备La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3高熵钙钛矿氧化物薄膜。
6)在75Torr氧压下冷却至室温,获得La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3高熵钙钛矿氧化物薄膜。
本实施例制备的La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3高熵钙钛矿氧化物薄膜成分为La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3高熵氧化物,且没有杂相。图1的X射线衍射图谱(XRD)所示,薄膜中除衬底和样品外无明显的第二相出现,为单相薄膜。图2的X射线反射图谱(XRR)显示出薄膜厚度约44-48nm。
本实施例制备的La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3薄膜具有优异的薄膜质量,且化学组分均一。图3的高分辨透射电镜图表明本实施例的La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3薄膜材料为单晶薄膜,与SrTiO3衬底处于完全共格关系。图3的Cr、Mn、Fe、Co、Ni各B位元素的电子能量损失图显示出各原子均分且随机分布,没有出现任何原子的团聚现象。
本实施例制备的La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3薄膜中Cr、Mn、Fe、Co、Ni各原子的价态由图4得出,其中Cr、Fe、Co均为+3价态,Mn和Ni分别为+4价态和+2价态。
本实施例制备的La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3单晶纯相薄膜显示出了垂直交换偏置特性。由图5可以得出,La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3薄膜在134K以下温度时表现为反铁磁性。在加3T大小的磁场冷却至10K后出现了沿着磁场方向的交换偏置特性。
实施例2
本实施例用于说明反铁磁性的La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3高熵钙钛矿氧化物薄膜与La0.67Sr0.33MnO3衬底形成的异质结具有明显的交换偏置效应。
按照实施例1的方法,不同之处在于:在SrTiO3衬底上先生长La0.67Sr0.33MnO3薄膜,随后在La0.67Sr0.33MnO3薄膜上生长La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3高熵钙钛矿氧化物薄膜,得到La0.67Sr0.33MnO3/La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3的异质结。
本实施例制备的La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3与La0.67Sr0.33MnO3异质结显示出明显的交换偏置效应。从图5的(c)部分表明,在加3T大小的磁场冷却至10K后,La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3与La0.67Sr0.33MnO3异质结表现出与冷却时所加磁场方向相同的交换偏置效应之外,还叠加有垂直的交换偏置效应。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (7)
1.一种高熵钙钛矿氧化物薄膜材料的制备方法,其特征在于,包括:
步骤S1,制备多晶La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3靶材:将La2O3、NiO、MnO2、Fe2O3、Co3O4和Cr2O3粉末混合,烧结后得到La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3靶材;
步骤S2,薄膜制备:采用La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3靶材,通过脉冲激光沉积的方法在衬底上进行薄膜沉积,得到高熵钙钛矿氧化物薄膜材料。
2.根据权利要求1所述的一种高熵钙钛矿氧化物薄膜材料的制备方法,其特征在于,步骤S1中,将La2O3、NiO、MnO2、Fe2O3、Co3O4和Cr2O3按照摩尔比混合均匀,通过烧结得到La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3陶瓷靶材。
3.根据权利要求1所述的一种高熵钙钛矿氧化物薄膜材料的制备方法,其特征在于,步骤S1中La2O3、NiO、MnO2、Fe2O3、Co3O4和Cr2O3的纯度为99.99%。
4.根据权利要求1所述的一种高熵钙钛矿氧化物薄膜材料的制备方法,其特征在于,步骤S2中所述脉冲激光沉积的参数为:温度600-650℃、激光能量密度为0.6-1.0J/cm2,氧压为50-150mTorr,脉冲频率为3-7Hz,沉积结束后在75Torr氧压下冷却至室温。
5.根据权利要求1所述的一种高熵钙钛矿氧化物薄膜材料的制备方法,其特征在于,步骤S2中所述衬底选自钙钛矿结构的LaAlO3、钙钛矿结构的SrTiO3、尖晶石结构的MgAl2O4或岩盐结构的MgO。
6.一种高熵钙钛矿氧化物薄膜材料,其特征在于,通过前述权利要求1-5任一项所述的制备方法获得。
7.一种新型的磁性材料,其特征在于,所述磁性材料为La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3(L5BO)。
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