CN108796474B - 一种基于溶液法同质外延MgO薄膜的制备方法 - Google Patents

一种基于溶液法同质外延MgO薄膜的制备方法 Download PDF

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CN108796474B
CN108796474B CN201810618364.4A CN201810618364A CN108796474B CN 108796474 B CN108796474 B CN 108796474B CN 201810618364 A CN201810618364 A CN 201810618364A CN 108796474 B CN108796474 B CN 108796474B
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陶伯万
马寅畅
赵睿鹏
唐浩
苟继涛
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1241—Metallic substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1291—Process of deposition of the inorganic material by heating of the substrate

Abstract

本发明属于薄膜制备技术领域，涉及在镀有IBAD‑MgO的金属基带上制备同质外延MgO薄膜的方法，具体为一种基于溶液法同质外延MgO薄膜的制备方法。本发明用低成本的溶液沉积法完全替代了传统高成本工艺复杂PVD方法，且制备的同质外延MgO薄膜表面形貌相比传统方法更优。

Description

一种基于溶液法同质外延MgO薄膜的制备方法
技术领域
本发明属于薄膜制备技术领域，涉及在镀有IBAD-MgO的金属基带上制备同质外延氧化镁（MgO）薄膜的方法，具体为一种基于溶液法同质外延MgO薄膜的制备方法。
背景技术
高温超导带材被广泛运用于电力传输、能源存储、传感器等诸多领域。双轴织构MgO缓冲层是高温超导带材的重要组成部分之一；制备平整度高、均一性好、取向一致性好的MgO缓冲层是制备高性能YBCO（钇钡铜氧）高温超导带材的前提，高质量、低成本、高效率的双轴织构MgO缓冲层制备技术对于高温超导带材的产业化具有重要意义。溶液沉积法因为具有高产量、低成本、工艺简单等优点，在高温超导带材领域中得到越来越多的关注。
目前高温超导带材的MgO缓冲层制备主流制备路线为：先利用离子束辅助沉积法（IBAD）在基带上沉积一层厚度为8~12nm的双轴织构MgO薄膜，然后通过物理气相沉积（PVD）的方法同质外延一层更厚的MgO薄膜，实现薄膜中晶粒取向的优化。但是通过PVD同质外延的工艺流程复杂，需要在高真空环境中进行，因此设备质量要求高，成本高，薄膜结构和形貌不够理想（均方根粗糙度大于3 nm）。
发明内容
针对上述存在的问题或不足，为了降低生产成本，提产品高性价比，优化薄膜表面形貌，本发明提供了一种基于溶液法同质外延MgO薄膜的制备方法。通过在金属基带上通电流的方式，使得金属基带本体能够均匀发热，实现MgO薄膜自下而上外延生长。采用溶液沉积法，使得薄膜表面平整致密，生产成本大幅降低。
技术方案如下：
步骤1、配置MgO前驱液：在0.1mol/L的氯化镁溶液中加入各占其质量百分比2.5%~3%的二乙醇胺和二乙烯三胺，并混合均匀，得到MgO前驱液。
步骤2、将已沉积8-12nm的IBAD-MgO的哈氏合金基带装入卷绕轮1中，其一端从卷绕轮1中拉出依次引入转轮1、转轮2、加热装置、转轮3后接入卷绕轮2中；步骤1所得MgO前驱液置于溶液池；转轮2位于溶液池内以调转基带在溶液中的移动方向。
步骤3、在加热装置对哈氏合金基带升温至500~600℃的条件下，卷绕轮2以100~150mm/min的速度牵引哈氏合金基带由卷绕轮1到转轮1，然后经过溶液池蘸取溶液并经转轮2调转方向后，垂直进入加热装置，最后被收集至卷绕轮2；即可制得同质外延MgO薄膜。
进一步的，所述步骤1中MgO前驱液制备后，再向其中加入占氯化镁溶液质量百分比0.5%~1%的冰醋酸再进行后续步骤，以防止Mg+水解，使得溶液体系稳定至少30天。
进一步的，所述加热装置为两组电极，电流从正极流入，通过分流电阻均分成n（n≥3）股电流从不同位置流入金属带材，同样均分成n股电流从负极流出。电极向基带输送电流，使得带材在焦耳效应的作用下温度升高并产生温度梯度，最终达到薄膜结晶条件，采用此种加热装置，可以使得薄膜由内向外结晶，生长出的薄膜拥有更好的织构。
本发明用低成本的溶液沉积法完全替代了传统高成本工艺复杂 PVD方法，且制备的同质外延MgO薄膜表面形貌相比传统方法更优。
附图说明
图1是实施例的溶液沉积装置示意图；
图2是实施例的加热装置示意图；
图3是实施例制备的MgO薄膜高能衍射电子枪（RHEED）衍射图案；
图4是实施例制备的MgO薄膜的原子力显微镜（AFM）测试图；
图5是MgO薄膜X射线光电子能谱（XPS）测试图。
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。
实施例：配置0.1mol/L的氯化镁酒精溶液作为MgO的前驱液，在镀有IBAD-MgO的10m金属基带上用化学溶液沉积法同质外延一层MgO薄膜。包括以下步骤：
步骤1、称量0.02mol的六水合氯化镁晶体4.6g，放入鼓风干燥箱烘烤恒温90℃烘烤4小时；
步骤2、将步骤1所得固体倒入200ml烧杯中，加无水乙醇定容至150ml，放入超声清洗器中，超声溶解30min，得到澄清透明的溶液；
步骤3、将步骤2所得溶液于烧杯中置于磁力搅拌器上，放入搅拌子，并开启加热模式加热至40℃，磁力搅拌2小时；
步骤4、向步骤3所得溶液加入1ml冰醋酸，并加入二乙醇胺和二乙烯三胺各5ml，加无水乙醇定容至200ml；
步骤5、向步骤4所得溶液放入搅拌子，磁力搅拌2小时使其混合均匀，得到稳定的MgO前驱液；该MgO前驱液在室温下密闭保存，此体系能稳定至少30天。
步骤6、准备、处理基带：将宽12mm、长10m已沉积10nm的IBAD-MgO哈氏合金基带，两端各焊接一条3m长的牵引基带，装入卷绕轮1中；
步骤7、将步骤5所得MgO前驱液置于溶液池中，将牵引带一端从卷绕轮1中拉出依次引入转轮1、溶液池中转轮2、加热电极、转轮3后装入提供牵引动力的卷绕轮2中；
步骤8、选用加热装置为两组电极，电流从正极流入，通过分流电阻均分成4股电流从不同位置流入金属带材，同样均分成4股电流从负极流出。电极向基带输送电流，使得带材在焦耳效应的作用下温度升高并产生温度梯度，最终达到薄膜结晶条件，采用此种自加热的加热装置，可以使得薄膜由内向外结晶，生长出的薄膜拥有更好的织构。
在加热电极向基带输送16A电流的条件下，卷绕轮2以120mm/min的牵引速度，牵引基带由卷绕轮1到转轮1，经过溶液池中转轮2，蘸取溶液后垂直进入加热电极，最后经转轮3被收集至卷绕轮2；即可制得同质外延MgO薄膜。
与哈氏合金基带接触的电极选摩擦力小、耐高温、导电性好的银钨合金棒，固定银钨合金棒的为弹性钢片，以确保基带与电极良好的接触。
上述步骤8制备好的同质外延MgO薄膜的XRD（X射线衍射）和AFM（原子力显微镜）的测试结果如下：
图3是实施例中MgO薄膜的（高能电子衍射）RHEED图案，表明MgO薄膜有良好的（100）面外取向和（110）面内取向。
图4是实施例中MgO薄膜原子力显微镜（AFM）的测试图，MgO颗粒分布均匀，表面平整致密无裂痕，其5mm×5mm范围类的均方根粗糙度（RMS）为0.594nm，可见其表面形貌平整度远好于通过常规方法制备的外延MgO薄膜。
图5是实施例中X射线光电子能谱（XPS）测试图，前驱液中的MgCl2已经充分受热分解为MgO，前驱液中的Cl元素以及添加剂（二乙醇胺、二乙烯三胺）中的C、N元素基本无残留。

Claims (2)

1.一种基于溶液法同质外延MgO薄膜的制备方法，具体步骤如下：
步骤1、配置MgO前驱液：在0.1mol/L的氯化镁溶液中加入各占其质量百分比2.5%~3%的二乙醇胺和二乙烯三胺，并混合均匀，得到MgO前驱液；
步骤2、将已沉积8-12nm的IBAD-MgO的哈氏合金基带装入卷绕轮（1）中，其一端从卷绕轮（1）中拉出依次引入转轮（1）、转轮（2）、加热装置、转轮（3）后接入卷绕轮（2）中；步骤1所得MgO前驱液置于溶液池；转轮（2）位于溶液池内以调转基带在溶液中的移动方向；
所述加热装置为两组电极，电流从正极流入，通过分流电阻均分成n股电流从不同位置流入金属带材，同样均分成n股电流从负极流出，n≥3；
步骤3、在加热装置对哈氏合金基带升温至500~600℃的条件下，卷绕轮（2）以100~150mm/min的速度牵引哈氏合金基带由卷绕轮（1）到转轮（1），然后经过溶液池蘸取溶液并经转轮（2）调转方向后，垂直进入加热装置，最后被收集至卷绕轮（2）；即可制得同质外延MgO薄膜。
2.如权利要求1所述基于溶液法同质外延MgO薄膜的制备方法，其特征在于：所述步骤1中MgO前驱液制备后，再向其中加入占氯化镁溶液质量百分比0.5%~1%的冰醋酸再进行后续步骤。
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