CN113087532B - 一种高性能NiZn铁氧体薄膜的制备方法 - Google Patents

一种高性能NiZn铁氧体薄膜的制备方法 Download PDF

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CN113087532B
CN113087532B CN202110238727.3A CN202110238727A CN113087532B CN 113087532 B CN113087532 B CN 113087532B CN 202110238727 A CN202110238727 A CN 202110238727A CN 113087532 B CN113087532 B CN 113087532B
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余忠
青豪
孙科
冉茂君
邬传健
刘海
蒋晓娜
兰中文
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University of Electronic Science and Technology of China
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Abstract

一种高性能NiZn铁氧体薄膜的制备方法，属于薄膜制备技术领域。包括：1)将亚硝酸钠、乙酸钠加入去离子水中，搅拌混合均匀，得到氧化反应液；2)将氯化亚铁、氯化镍、氯化锌、氯化钴加入去离子水中，搅拌混合均匀，得到还原反应液；3)将干净的基板放置于旋转喷涂设备的加热板中央，调节基板温度、旋转速度、氧化反应液和还原反应液的供应速率、超声雾化功率，沉积薄膜。本发明通过减少主配方中Fe含量并引入Co，降低了薄膜面内磁各向异性，提高NiZn铁氧体薄膜起始磁导率的同时还兼具高的截止频率和饱和磁化强度，为磁性薄膜应用于片上***的电感器和高频开关电源提供了有效方法。

Description

一种高性能NiZn铁氧体薄膜的制备方法
技术领域
本发明属于薄膜制备技术领域，具体涉及一种高性能NiZn铁氧体薄膜的低温制备方法。
背景技术
近年来，电子信息产品往高频化、小型化、集成化方面快速发展，特别是随着半导体工艺地不断进步，电子电路的集成度也日益提升。作为无源器件的电阻器和电容器已经能够进行薄膜化，从而在电子***中集成应用。然而，作为三大无源器件之一的电感器，却因为传统磁性材料庞大的体积和质量，限制了其在电路***中的集成化发展。因此，高性能软磁薄膜的发展需求变得日益迫切。NiZn铁氧体薄膜具有高电阻率、高居里温度、优良的机械耐磨性及稳定的化学性能等优点，是在高频磁性器件中广泛应用的软磁薄膜。
考虑到高频磁性器件的应用需求，NiZn铁氧体薄膜通常需要高磁导率和高截止频率，前者是磁性器件具有良好性能的前提，后者决定了磁性器件的工作频率。然而，一般情况下高磁导率和高截止频率很难同时兼顾，这也是制约NiZn铁氧体薄膜应用的因素之一。
目前，制备NiZn铁氧体薄膜的方法主要有磁控溅射法、激光脉冲沉积法、溶胶-凝胶法等，这些方法通常需要高温热处理(800℃以上)，而硅基集成电路基板的最大承受温度一般不超过400℃，因此这些薄膜制备技术不能与半导体工艺兼容。旋转喷涂法作为一种低温沉积薄膜技术，不仅具有工艺简单、沉积速度较快等优点，更重要的是其反应所需要的加热温度不超过150℃(实际成膜温度低于100℃)，整个工艺流程能与硅基集成电路的半导体工艺相兼容，受到了科研人员的广泛关注。Matsushita N等人(Matsushita N,Chong C P,Mizutani T,et al.Ni–Zn ferrite films with high permeability(μ′＝～30,μ″＝～30)at 1GHz prepared at90℃[J].Journal of Applied Physics,2002,91(10):7376-7378.)通过旋转喷涂法在90℃的玻璃基板上制备了主配方为Ni0.21Zn0.19Fe2.60O4的NiZn铁氧体薄膜，得到的薄膜的截止频率fr高达1.2GHz，而起始磁导率μ′最大仅为42。中国专利CN109852929A公开了一种NiZn铁氧体薄膜的制备方法，其先采用旋转喷涂法在玻璃基片上制备NiZn铁氧体种子层，再采用射频磁控溅射法在种子层上沉积NiZn铁氧体薄膜，最终得到的NiZn铁氧体薄膜具有起始磁导率μ′≥200和截止频率fr≥1.85GHz的优异性能。但是，该方法工艺复杂，反应时间长，不利于推广应用。
发明内容
本发明的目的在于，针对背景技术存在的缺陷，提出了一种高性能NiZn铁氧体薄膜的制备方法，该方法得到的NiZn铁氧体薄膜兼具低矫顽力、高磁导率和高截止频率特性。
为实现上述目的，本发明采用的技术方案如下：
一种高性能NiZn铁氧体薄膜的制备方法，其特征在于，包括以下步骤：
步骤1、配制氧化反应液和还原反应液：
1.1将亚硝酸钠、乙酸钠加入去离子水中，搅拌混合均匀，得到氧化反应液，氧化反应液中，亚硝酸钠的浓度为0.1g/L～0.2g/L，乙酸钠的浓度为1.3g/L～1.5g/L；
1.2将氯化亚铁、氯化镍、氯化锌、氯化钴加入去离子水中，搅拌混合均匀，得到还原反应液，还原反应液中，氯化亚铁、氯化镍、氯化锌和氯化钴的摩尔比为(12.83～13.97)：(0.61～2.83)：1：(0.11～0.67)，氯化亚铁的浓度为1.3g/L～1.6g/L；
步骤2、将干净的基板放置于旋转喷涂设备的加热板中央，在基板温度为90～95℃、旋转速度为100～120r/min、氧化反应液的供应速率为10mL/min～20mL/min、还原反应液的供应速率为10mL/min～20mL/min、超声雾化功率为2～3W、空气气压为2MPa～3MPa的条件下，沉积20min～60min，即可得到所述高性能NiZn铁氧体薄膜。
进一步地，步骤2得到的高性能NiZn铁氧体薄膜的厚度为1μm～3μm。
本发明方法得到的高性能NiZn铁氧体薄膜，其性能指标为：
(1)高起始磁导率：μ′(100MHz)≥80(25℃)；
(2)高截止频率：fr≥150MHz(25℃)；
(3)高饱和磁化强度：4πMs≥4500Gs(25℃)；
(4)低矫顽力：Hc≤15Oe(25℃)；
与现有技术相比，本发明的有益效果为：
1、本发明提供的一种高性能NiZn铁氧体薄膜的制备方法，通过减少主配方中Fe含量并引入Co，降低了薄膜面内磁各向异性，提高NiZn铁氧体薄膜起始磁导率的同时还兼具高的截止频率和饱和磁化强度，为磁性薄膜应用于片上***(SOC)的电感器和高频开关电源提供了有效方法。
2、本发明提供的一种高性能NiZn铁氧体薄膜的制备方法，反应温度控制在90～95℃，且无需后续高温热处理过程，可实现与半导体工艺的兼容。
附图说明
图1为本发明实施例1制得的NiZn铁氧体薄膜的XRD图谱；
图2为本发明对比例制得的NiZn铁氧体薄膜的XRD图谱；
图3为本发明实施例1制得的NiZn铁氧体薄膜的SEM图；
图4为本发明对比例制得的NiZn铁氧体薄膜的SEM图；
图5为本发明实施例1制得的NiZn铁氧体薄膜的磁滞回线；
图6为本发明对比例制得的NiZn铁氧体薄膜的磁滞回线；
图7为本发明实施例1制得的NiZn铁氧体薄膜的磁谱图；
图8为本发明对比例制得的NiZn铁氧体薄膜的磁谱图。
具体实施方式
下面结合附图和实施例，详述本发明的技术方案。
一种高性能NiZn铁氧体薄膜的制备方法，其特征在于，包括以下步骤：
步骤1、依次采用无水乙醇、丙酮清洗基板，自然晾干；
步骤2、配制氧化反应液和还原反应液：
2.1将亚硝酸钠、乙酸钠加入去离子水中，搅拌混合均匀，得到氧化反应液，氧化反应液中，亚硝酸钠的浓度为0.1g/L～0.2g/L，乙酸钠的浓度为1.3g/L～1.5g/L；
2.2将氯化亚铁、氯化镍、氯化锌、氯化钴加入去离子水中，搅拌混合均匀，得到还原反应液，还原反应液中，氯化亚铁、氯化镍、氯化锌和氯化钴的摩尔比为(12.83～13.97)：(0.61～2.83)：1：(0.11～0.67)，氯化亚铁的浓度为1.3g/L～1.6g/L；
步骤3、将步骤1清洗后的基板放置于旋转喷涂设备的加热板中央，向旋转喷涂设备中通入纯净干燥的空气，空气气压为2MPa～3MPa；调整超声波雾化功率，使反应液以喷雾形式落在加热板上，超声雾化功率为2～3W；调整反应喷嘴流量，控制氧化反应液的供应速率为10mL/min～20mL/min、还原反应液的供应速率为10mL/min～20mL/min；调整反应台转速，控制旋转速率为100～120r/min；调整加热板温度，控制基板温度为90～95℃；
步骤4、开启加热装置，对基片进行预热20min～30min；将步骤2配制的氧化反应液和还原反应液接入反应装置，进行旋转喷涂，反应时间为20min～60min，制得的高性能NiZn铁氧体薄膜的厚度为1μm～3μm。
步骤5、对步骤4得到的NiZn铁氧体薄膜进行测试：采用X射线衍射仪表征薄膜样品的物相结构；采用扫描电子显微镜(SEM)观察薄膜样品的显微结构；采用振动样品磁强计(VSM)测量薄膜样品的饱和磁化强度及矫顽力；采用矢量网络分析仪测量薄膜样品磁谱曲线。
实施例1
一种高性能NiZn铁氧体薄膜的制备方法，其特征在于，包括以下步骤：
步骤1、依次采用无水乙醇、丙酮清洗PI基板，自然晾干；
步骤2、配制氧化反应液和还原反应液：
2.1将亚硝酸钠、乙酸钠加入去离子水中，搅拌混合均匀，得到氧化反应液，氧化反应液中，亚硝酸钠的浓度为0.1506g/L，乙酸钠的浓度为1.4257g/L；
2.2将氯化亚铁、氯化镍、氯化锌、氯化钴加入去离子水中，搅拌混合均匀，得到还原反应液，还原反应液中，氯化亚铁、氯化镍、氯化锌和氯化钴的摩尔比为12.86：2.28：1：0.28，氯化亚铁的浓度为1.3076g/L；
步骤3、将步骤1清洗后的基板放置于旋转喷涂设备的加热板中央，向旋转喷涂设备中通入纯净干燥的空气，空气气压为2.4MPa；调整超声波雾化功率，使反应液以喷雾形式落在加热板上，超声雾化功率为2.8W；调整反应喷嘴流量，控制氧化反应液的供应速率为15mL/min、还原反应液的供应速率为15mL/min；调整反应台转速，控制旋转速率为120r/min；调整加热板温度，控制基板温度为90℃；
步骤4、开启加热装置，对PI基片进行预热20min；将步骤2配制的氧化反应液和还原反应液接入反应装置，进行旋转喷涂，反应时间为20min，制得的高性能NiZn铁氧体薄膜的厚度为1μm。
步骤5、对步骤4得到的NiZn铁氧体薄膜进行测试：采用X射线衍射仪表征薄膜样品的物相结构；采用扫描电子显微镜(SEM)观察薄膜样品的显微结构；采用振动样品磁强计(VSM)测量薄膜样品的饱和磁化强度及矫顽力；采用矢量网络分析仪测量薄膜样品磁谱曲线。
实施例2
本实施例与实施例1相比，区别在于：步骤2中，配制还原反应液时，氯化亚铁、氯化镍、氯化锌和氯化钴的摩尔比为13.42：1.72：1：0.28，氯化亚铁的浓度为1.3693g/L；其余步骤与实施例1相同。
实施例3
本实施例与实施例1相比，区别在于：步骤2中，配制还原反应液时，氯化亚铁、氯化镍、氯化锌的摩尔比为13.97：1.17：1：0.56，氯化亚铁的浓度为1.4261g/L；其余步骤与实施例1相同。
实施例4
本实施例与实施例1相比，区别在于：步骤2中，配制还原反应液时，氯化亚铁、氯化镍、氯化锌和氯化钴的摩尔比为12.83：2.31：1：0.28，氯化亚铁的浓度为1.3076g/L；其余步骤与实施例1相同。
对比例
步骤1、依次采用无水乙醇、丙酮清洗PI基板，自然晾干；
步骤2、配制氧化反应液和还原反应液：
2.1将亚硝酸钠、乙酸钠加入去离子水中，搅拌混合均匀，得到氧化反应液，氧化反应液中，亚硝酸钠的浓度为0.1506g/L，乙酸钠的浓度为1.4257g/L；
2.2将氯化亚铁、氯化镍、氯化锌加入去离子水中，搅拌混合均匀，得到还原反应液，还原反应液中，氯化亚铁、氯化镍、氯化锌的摩尔比为15.06：2.83：1，氯化亚铁的浓度为1.5398g/L；
步骤3、将步骤1清洗后的基板放置于旋转喷涂设备的加热板中央，向旋转喷涂设备中通入纯净干燥的空气，空气气压为2.4MPa；调整超声波雾化功率，使反应液以喷雾形式落在加热板上，超声雾化功率为2.8W；调整反应喷嘴流量，控制氧化反应液的供应速率为15mL/min、还原反应液的供应速率为15mL/min；调整反应台转速，控制旋转速率为120r/min；调整加热板温度，控制基板温度为90℃；
步骤4、开启加热装置，对PI基片进行预热20min；将步骤2配制的氧化反应液和还原反应液接入反应装置，进行旋转喷涂，反应时间为20min，制得的高性能NiZn铁氧体薄膜的厚度为1μm。
图1和图2分别为实施例1和对比例薄膜样品的XRD图谱，结果显示实施例1得到的薄膜样品的晶相倾向于沿(222)取向。
图3和图4分别为实施例1和对比例薄膜样品的SEM图，结果显示实施例1样品晶粒呈三角形，与(222)取向吻合，且晶粒尺寸分别为0.2与0.5μm，可知，得到的NiZn铁氧体薄膜的晶粒更加细化、均匀。
图5和图6分别为实施例1和对比例薄膜样品的磁滞回线图，结果显示实施例1得到的NiZn铁氧体薄膜样品的矫顽力Hc减小。
图7和图8分别为实施例1和对比例薄膜样品的磁谱图，结果显示实施例1得到的NiZn铁氧体薄膜样品虽然截止频率会降低，但是磁导率大幅提高，矫顽力下降。
实施例与对比例得到的薄膜样品的测试结果如下表：
Figure BDA0002961316840000061

Claims (2)

1.一种高性能NiZn铁氧体薄膜的制备方法，其特征在于，包括以下步骤：
步骤1、配制氧化反应液和还原反应液：
1.1将亚硝酸钠、乙酸钠加入去离子水中，搅拌混合均匀，得到氧化反应液，氧化反应液中，亚硝酸钠的浓度为0.1g/L～0.2g/L，乙酸钠的浓度为1.3g/L～1.5g/L；
1.2将氯化亚铁、氯化镍、氯化锌、氯化钴加入去离子水中，搅拌混合均匀，得到还原反应液，还原反应液中，氯化亚铁、氯化镍、氯化锌和氯化钴的摩尔比为(12.83～13.97)：(0.61～2.83)：1：(0.11～0.67)，氯化亚铁的浓度为1.3g/L～1.6g/L；
步骤2、将干净的基板放置于旋转喷涂设备的加热板中央，在基板温度为90～95℃、旋转速度为100～120r/min、氧化反应液的供应速率为10mL/min～20mL/min、还原反应液的供应速率为10mL/min～20mL/min、超声雾化功率为2～3W、空气气压为2MPa～3MPa的条件下，沉积20min～60min，即可得到所述高性能NiZn铁氧体薄膜。
2.根据权利要求1所述的高性能NiZn铁氧体薄膜的制备方法，其特征在于，步骤2得到的高性能NiZn铁氧体薄膜的厚度为1μm～3μm。
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