CN115537738B - 一种高剩磁比高矫顽力的m型铁氧体异质结薄膜的制备方法 - Google Patents
一种高剩磁比高矫顽力的m型铁氧体异质结薄膜的制备方法 Download PDFInfo
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- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 36
- 229910002367 SrTiO Inorganic materials 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims description 23
- 238000000151 deposition Methods 0.000 claims description 21
- 230000008021 deposition Effects 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 238000000137 annealing Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- 230000005415 magnetization Effects 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 5
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 229910002370 SrTiO3 Inorganic materials 0.000 abstract description 11
- 238000004549 pulsed laser deposition Methods 0.000 abstract description 10
- 239000005084 Strontium aluminate Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
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- AJCDFVKYMIUXCR-UHFFFAOYSA-N oxobarium;oxo(oxoferriooxy)iron Chemical compound [Ba]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O AJCDFVKYMIUXCR-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明公开了一种高剩磁比高矫顽力的M型铁氧体异质结薄膜的制备方法，该方法选用了SrTiO3(111)衬底，Sr3Al2O6作为缓冲层，得到结构为BaFe12O19(0001)/Sr3Al2O6/SrTiO3的异质结薄膜。其制备方法包括以下步骤：（1）使用脉冲激光沉积系统（PLD）在SrTiO3(111)衬底上沉积作为缓冲层的Sr3Al2O6薄膜。（2）使用脉冲激光沉积系统在Sr3Al2O6/SrTiO3异质结结构上沉积M型铁氧体BaFe12O19薄膜。本实验以Sr3Al2O6作为缓冲层，制备了BaFe12O19(0001)/Sr3Al2O6/SrTiO3异质结薄膜。后续的磁性结果显示，材料的剩磁比高达0.97，矫顽力增加至15 kOe，这使得该材料在微波吸收、垂直磁记录、永磁等方面具有广阔的应用前景。
Description
技术领域
本发明涉及一种高剩磁比高矫顽力的M型铁氧体异质结薄膜的制备方法，具体涉及一种矫顽力为12-15 kOe、饱和磁化强度为60-70 emu/cm3、剩磁比为0.90-0.97的BaFe12O19(0001)/Sr3Al2O6/SrTiO3异质结薄膜的制备方法。
背景技术
随着科学技术的发展，下一代微波器件，如环行器、隔离器、移相器和滤波器等，要求应用于其中的铁氧体材料具有片式、非互易、自偏置、低损耗等特点。M型铁氧体由于具有大的垂直磁晶各向异性、较高的饱和磁化强度、较高的矫顽力、较强的单轴磁晶各向异性场、高电阻率和介电常数、良好的化学稳定性和机械强度等特点，被认为是下一代微波铁氧体器件中最具应用潜力的材料之一。同时，M型铁氧体的这些特点使其在垂直磁记录材料等方面也具有巨大的应用前景。
尽管M 型钡铁氧体具有上述优势，然而如何开发一种制备高质量M型铁氧体薄膜的方法。一直是目前困扰该材料投入实际使用中的一个重大难题。为了解决这一问题许多研究者都相继投入到了M型钡铁氧体的相关制备研究之中。
在20世纪70年代，Glass等利用液相外延（LEP）的方法制备出了M型铁氧体的单晶薄膜，但是并未对其磁性能有所研究。1992年，Dorsey等用脉冲激光沉积（PLD）的方法制备了具有沿c轴取向的BaFe12O19薄膜，虽提高了铁磁共振线宽性能，但剩磁比非常低。随后，Sui等利用磁控溅射沉积BaFe12O19薄膜，其剩磁比达到了0.63，矫顽力为4.1 kOe。2002年，Wang等同样使用LEP技术沉积了BaFe12O19的厚膜（45 μm），但是剩磁比和矫顽力却很低，达不到器件应用的要求。紧接着，Song等利用PLD方法在蓝宝石单晶衬底（Al2O3）上沉积了c轴取向的BaFe12O19薄膜，其剩磁等方面的性能有所提高，但剩磁比依旧很低，只有0.3。近些年来，Wei等通过PLD沉积了自组装纳米岛状的BaFe12O19薄膜，其剩磁比为0.1左右。Mohebbi等原位沉积了具有沿c轴取向的BaFe12O19薄膜，提高了薄膜的电阻率，其矫顽力和饱和磁化强度与块体的相近，剩磁比为0.37。Zheng等用PLD法在Pt(111)/Al2O3(0001)上沉积了矫顽力为1 kOe的BaFe12O19薄膜，但是剩磁比仅有0.3。
综上所述，BaFe12O19薄膜的矫顽力与剩磁比均较小。因此，近几年来，相关研究学者探究了增加缓冲层对BaFe12O19薄膜性能的影响，发现缓冲层的存在可以明显提高其性能。Koichi Kakizaki等在室温下用射频溅射法制备了以AlN作为缓冲层的BaFe12O19薄膜，矫顽力达到了7 kOe。Nobuhiro Matsushita等在Si衬底上制备BaFe12O19/Pt多层复合薄膜以提高BaFe12O19薄膜的磁性能，矫顽力和剩磁比分别达到了2 kOe和0.6。S. Salemizadeh等使用Al2O3作为薄膜缓冲层在Si(110)衬底上沉积了矫顽力为4.9 kOe、剩磁比为0.61的BaFe12O19薄膜。X. H. Liu等在Si衬底上以MgO作为缓冲层制备了BaFe12O19薄膜，薄膜的面内剩磁比为0.2，面外剩磁比为0.5，矫顽力为1.4 kOe。
根据目前研究结果可知，增加缓冲层有效的提高了矫顽力及剩磁比，但离实际应用还有一定距离，因此，对于制备出高的矫顽力、高的饱和磁化强度和大的剩磁比的薄膜仍是我们需要努力的一个方向。
发明内容
本发明的目的是提供一种高剩磁比高矫顽力的M型铁氧体异质结薄膜的制备方法，显著增大了其室温剩磁比和矫顽力，可以提高其在微波吸收领域、垂直磁记录等方面的应用。
为了达到上述目的，发明了一种高剩磁比高矫顽力的M型铁氧体异质结薄膜的制备方法，该方法首次将缓冲层Sr3Al2O6加入到SrTiO3(111)衬底和目标薄膜BaFe12O19(0001)之间，构成BaFe12O19(0001)/Sr3Al2O6/SrTiO3异质结薄膜，并通过调控沉积薄膜时的衬底温度、氧气压强、激光能量和镀膜时间等因素，获取BaFe12O19(0001)/Sr3Al2O6/SrTiO3异质结薄膜，以获得优良的矫顽力，剩磁比以及饱和磁化强度。
一种高剩磁比高矫顽力的M型铁氧体异质结薄膜的制备方法，包括以下步骤：
（1）靶材制备：使用纯度为99.9 %以上的SrCO3、Al2O3、BaCO3和Fe2O3制备用于脉冲激光沉积的Sr3Al2O6与BaFe12O19的靶材；
（2）薄膜沉积：将SrTiO3(111)衬底、BaFe12O19靶材与Sr3Al2O6靶材置于PLD样品腔内，使用脉冲激光沉积的方法首先在SrTiO3(111)衬底上沉积Sr3Al2O6薄膜，然后沉积BaFe12O19薄膜；
（3）原位退火：将样品腔内条件设置为600 ℃、1-2 kPa氧压，在此条件下保持120min，然后缓慢降至室温；
（4）马弗炉退火：将沉积完成的薄膜置于马弗炉中退火，温度为1100 ℃，时间60min，以保证薄膜的生长。
其中，步骤（1）所述Sr3Al2O6靶材的制备方法，包括如下步骤：
1）靶材所用原料是纯度分别为99.95 %和99.99 %的SrCO3和Al2O3粉末药品，按照样品的原子摩尔比进行配比；
2）使用行星式球磨机将原料混合成为均匀细小的粉末；
3）将球磨得到的粉末置于箱式炉中进行煅烧，煅烧温度为1100 ℃，煅烧时间为20h；
4）将煅烧之后的样品进行研磨，然后加入PVA作为粘结剂，研磨至均匀细小的粉末之后将其加入模具中压制成为靶材胚体；
5）将靶材胚体在箱式炉中进行烧结，烧结温度为1350 ℃，烧结时间为24 h，即可得到所需的靶材，得到的靶材需要干燥收置，防止受潮。
其中，步骤（1）所述BaFe12O19靶材的制备方法，包括如下步骤：
1）靶材所用原料是纯度分别为99.95 %和99.9 %的BaCO3和Fe2O3粉末药品，按照样品的原子摩尔比进行配比；
2）使用行星式球磨机将原料研磨成为均匀细小的粉末；
3）将球磨得到的粉末置于箱式炉中进行煅烧，煅烧温度为1100 ℃，煅烧时间为10h；
4）将煅烧之后的样品进行研磨，然后加入PVA作为粘结剂，研磨至均匀细小的粉末之后将其加入模具中压制成为靶材胚体；
5）将靶材胚体在箱式炉中进行烧结，烧结温度为1250 ℃，烧结时间为20 h，即可得到所需的靶材。
步骤（2）所述SrTiO3(111)衬底为单晶基片，晶面为(111)，得到的是(0001)取向的M型铁氧体薄膜。
步骤（2）所述Sr3Al2O6薄膜的沉积过程中衬底温度为720 ℃，激光能量为300 mJ，激光频率为2 Hz，沉积时间为5 min，在沉积过程中的氧压约为1 Pa。
步骤（2）所述BaFe12O19薄膜的沉积过程中衬底温度为650-720 ℃，激光能量为250-300 mJ，激光频率为5-10 Hz，沉积时间为20-30 min，在沉积过程中氧压为10-20 Pa。
步骤（2）所述沉积过程中，靶材与衬底的间距为33-36 mm，靶材与衬底互为逆向转动。
本发明的有益效果是：
（1）未加Sr3Al2O6缓冲层时，面外的剩磁比在10 K和300 K温度下约为0.22和0.25，而加入缓冲层之后约为0.81和0.97，显著增大了剩磁比。
（2）加入了Sr3Al2O6缓冲层之后，垂直于薄膜面内方向的矫顽力在10 K时为12kOe，在300 K时达到了15 kOe，是未加缓冲层时的十几倍。
（3）X射线衍射图谱显示，所有的衍射峰沿（0001）取向，表明薄膜具有良好的取向性。
（4）PLD是非常成熟的制膜技术，可以高效、可控的生长出所需要的薄膜，并且制备过程简单，周期较短。
附图说明
图1为实例1所制备的BaFe12O19(0001)/Sr3Al2O6/SrTiO3异质结薄膜样品的X射线衍射图谱。
图2为实例1所制备的BaFe12O19(0001)/Sr3Al2O6/SrTiO3异质结薄膜样品在300 K温度下的面外的磁滞回线（磁化强度（M）随磁场（H）的变化曲线）。
具体实施方式
本发明通过实施例，结合说明书附图对本发明内容作进一步详细说明，但不是对本发明的限制。
实施例1
一种高剩磁比高矫顽力的M型铁氧体异质结薄膜的制备方法：
（1）制备Sr3Al2O6靶材：
将纯度为99.95 %的SrCO3和纯度为99.99 %的Al2O3根据相应原子比进行计算、称量，然后使用行星式球磨机进行球磨（转速为300 r/min），球磨之后将其置于80 ℃干燥箱中进行干燥，彻底干燥后使用100目的筛子进行过筛，然后将过筛后的粉末置于箱式炉中于1100 ℃煅烧20 h，取出后加入PVA进行研磨，然后将其压制成直径为24 mm、厚度为3 mm的片子，将片子置于箱式炉中在1350 ℃下烧结24 h，即可得到镀膜需要的靶材。
（2）制备BaFe12O19靶材：
将纯度为99.95 %的BaCO3和纯度为99.9 %的Fe2O3根据相应原子比进行计算、称量，然后用行星式球磨机进行球磨（转速为300 r/min），球磨之后将其置于80 ℃干燥箱中进行干燥，彻底干燥后使用100目的筛子进行过筛，然后将过筛后的粉末置于箱式炉中于1100 ℃煅烧10 h，取出后加入PVA进行研磨，然后将其压制成直径为24 mm、厚度为3 mm的片子，将片子置于箱式炉中在1250 ℃下烧结20 h，即可得到镀膜需要的靶材。
（3）清洗衬底：
镀膜使用的衬底首先使用丙酮超声清洗10 min，然后用酒精超声清洗10 min，最后使用去离子水超声清洗10 min。
（4）使用高温胶将清洗完成的衬底粘到样品托上，将衬底和靶材安置到样品腔内。
（5）在SrTiO3(111)衬底上沉积Sr3Al2O6薄膜，将样品腔温度升至720 ℃，氧压控制在1 Pa左右，调节激光能量为300 mJ、激光频率为2 Hz、衬底与靶材的间距为33 mm，然后沉积Sr3Al2O6薄膜5 min。
（6）在Sr3Al2O6/SrTiO3异质结上沉积BaFe12O19薄膜，样品腔温度保持在720 ℃，氧压为15 Pa，激光能量为300 mJ，激光频率为7 Hz，衬底与靶材的间距为33 mm，然后沉积BaFe12O19薄膜20 min。
（7）沉积完成后将样品腔内的氧压调整至2 kPa，设置样品腔温度为600 ℃，保持120 min，然后逐渐降温至室温。
（8）将沉积完成的薄膜置于箱式炉中进行退火处理，退火条件为1100 ℃、60 min，该薄膜制备完毕。
实施例2
一种高剩磁比高矫顽力的M型铁氧体异质结薄膜的制备方法：
（1）清洗衬底
镀膜使用的衬底首先使用丙酮超声清洗10 min，然后用酒精超声清洗10 min，最后使用去离子水超声清洗10 min。
（2）使用高温胶将清洗完成的衬底粘到样品托上，将衬底和靶材安置到样品腔内。
（3）在SrTiO3(111)衬底上沉积Sr3Al2O6薄膜，将样品腔温度升至720 ℃，氧压控制在1 Pa左右，调节激光能量为300 mJ、激光频率为2 Hz、衬底与靶材的间距为33 mm，然后沉积Sr3Al2O6薄膜5 min。
（4）在Sr3Al2O6/SrTiO3上沉积BaFe12O19薄膜，样品腔温度保持在720 ℃，氧压为15Pa，激光能量为300 mJ，激光频率为7 Hz，衬底与靶材的间距为33 mm，然后沉积BaFe12O19薄膜30 min。
（5）沉积完成后将样品腔内的氧压调整至2 kPa，设置样品腔温度为600 ℃，保持120 min，然后逐渐降温至室温。
（6）将沉积完成的薄膜置于箱式炉中进行退火处理，退火条件为1100 ℃、60 min，BaFe12O19(0001)/Sr3Al2O6/SrTiO3异质结薄膜制备完毕。
对实施例1制备得到的M型铁氧体异质结薄膜进行表征：
（1）X射线衍射表征：如图1所示，X射线衍射结果表明，图谱中出现的峰都是(0001)晶向的取向峰，说明制备的样品为单一取向的薄膜。
（2）磁性能测试：如图2所示是室温下该异质结薄膜的磁滞回线，剩磁比为0.97左右，矫顽力的大小为15 kOe左右，证明我们制备出了高剩磁比高矫顽力的M型铁氧体异质结薄膜。
Claims (7)
1.一种高剩磁比高矫顽力的M型铁氧体异质结薄膜的制备方法，其特征在于，将BaFe12O19与Sr3Al2O6结合，具体包括如下步骤：
（1）靶材制备：使用纯度为99.9 %以上的SrCO3、Al2O3、BaCO3和Fe2O3制备用于脉冲激光沉积的Sr3Al2O6与BaFe12O19的靶材；
（2）薄膜沉积：将SrTiO3(111)衬底、BaFe12O19靶材与Sr3Al2O6靶材置于PLD样品腔内，使用脉冲激光沉积的方法首先在SrTiO3(111)衬底上沉积Sr3Al2O6薄膜，然后沉积BaFe12O19薄膜，上述SrTiO3(111)衬底为单晶基片，晶面为(111)，得到的是(0001)取向的M型铁氧体BaFe12O19薄膜；
（3）原位退火：将样品腔内条件设置为600 ℃、1-2 kPa氧压，在此条件下保持120 min，然后缓慢降至室温；
（4）马弗炉退火：将沉积完成的薄膜置于马弗炉中退火，温度为1100 ℃，时间60 min，以保证薄膜的生长。
2.根据权利要求1所述的制备方法，其特征在于，步骤（1）所述Sr3Al2O6靶材的制备方法，包括如下步骤：
1）将纯度分别为99.95 %和99.99 %的SrCO3和Al2O3粉末按照化合物Sr3Al2O6的原子摩尔比进行配比；
2）使用行星式球磨机对原料进行混合研磨；
3）将球磨得到的粉末置于箱式炉中进行煅烧，煅烧温度为1100 ℃，煅烧时间为20 h；
4）将煅烧之后的样品进行研磨，然后加入PVA作为粘结剂，研磨至均匀细小的粉末之后将其加入模具中压制成靶材胚体；
5）将靶材胚体在箱式炉中进行烧结，烧结温度为1350 ℃，烧结时间为24 h，即可得到所需的靶材，得到的靶材需要干燥收置，防止受潮。
3.根据权利要求1所述的制备方法，其特征在于，步骤（1）所述BaFe12O19靶材的制备方法，包括如下步骤：
1）将纯度分别为99.95 %和99.9 %的BaCO3和Fe2O3粉末按照BaFe12O19的原子摩尔比进行配比；
2）使用行星式球磨机将原料进行混合研磨；
3）将球磨得到的粉末置于箱式炉中进行煅烧，煅烧温度为1100 ℃，煅烧时间为10 h；
4）将煅烧之后的样品进行研磨，然后加入PVA作为粘结剂，研磨至均匀细小的粉末之后将其加入模具中压制成为靶材胚体；
5）将靶材胚体在箱式炉中进行烧结，烧结温度为1250 ℃，烧结时间为20 h，即可得到所需的靶材。
4.根据权利要求1所述的制备方法，其特征在于，步骤（2）所述Sr3Al2O6薄膜的沉积过程中衬底温度为720 ℃，激光能量为300 mJ，激光频率为2 Hz，沉积时间为5 min，氧压约为1Pa。
5.根据权利要求1所述的制备方法，其特征在于，步骤（2）所述BaFe12O19薄膜的沉积过程中衬底温度为650-720 ℃，激光能量为250-300 mJ，激光频率为5-10 Hz，沉积时间为20-30min，氧压为10-20 Pa。
6.根据权利要求1所述的制备方法，其特征在于，步骤（2）所述沉积过程中，靶材与衬底的间距为33-36 mm，靶材与衬底互为逆向转动。
7. 用权利要求1-6任意一项所述的制备方法制备的高剩磁比高矫顽力的M型铁氧体异质结薄膜，该异质结薄膜的剩磁比范围为0.90-0.97，矫顽力为12-15 kOe，饱和磁化强度为60-70 emu/cm3。
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