CN112608151A - 一种超薄铌酸钾钠基柔性压电薄膜材料及其制备方法 - Google Patents

一种超薄铌酸钾钠基柔性压电薄膜材料及其制备方法 Download PDF

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CN112608151A
CN112608151A CN202010533408.0A CN202010533408A CN112608151A CN 112608151 A CN112608151 A CN 112608151A CN 202010533408 A CN202010533408 A CN 202010533408A CN 112608151 A CN112608151 A CN 112608151A
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龚文
谭祥虎
姚方周
吴超峰
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Foshan Southern China Institute For New Materials
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Abstract

本发明提出一种超薄铌酸钾钠基柔性压电薄膜材料及其制备方法，化学分子式为：(1‑x)(K0.48Na0.48Li0.02) Nb0.8Ta0.2O3‑xLn(Zr1‑y Ti y )O3 (KNN‑LT)，其中Ln为Ca，Ba及Sr中的一种或多种；x和y为摩尔数，0<x<0.1，0≤y≤1。采用激光分子束外延法（Laser Molecular Beam Epitaxy，LMBE）,利用水溶性的Sr3Al2O6作为牺牲层制备超薄柔性压电薄膜。制备的KNN‑LT靶材性能优良且稳定，可满足正常使用需求。制备的柔性薄膜表面平整、组分精确、柔性好、厚度薄可接近临界厚度及制备合格率高。

Description

一种超薄铌酸钾钠基柔性压电薄膜材料及其制备方法
技术领域
本发明涉及无铅压电陶瓷技术领域，尤其涉及一种超薄铌酸钾钠基柔性压电薄膜材料及其制备方法。
背景技术
柔性压电薄膜因为其优异的性能被广泛用于柔性传感器、存储器、储能设备、植入式生物医疗电子、可卷曲电子显示屏等领域。但是随着纳米技术及生物探测技术的快速发展，对压电薄膜在厚度以及性能上的要求越来越高。目前，柔性压电薄膜的主要制备方法有脉冲沉积法、磁控溅射法、溶胶凝胶等方法，但是上述方法在厚度和性能上很难再有突破。西安交大刘明教授等人利用激光分子束外延法（Laser Molecular Beam Epitaxy，LMBE）制备了性能优良的自支撑的单晶胞层厚度的SrTiO3薄膜，目前鲜有报道将此技术应用到制备性能优良的超薄压电薄膜。因此，可尝试用LMBE法制备超薄压电薄膜。
锆钛酸铅（PZT）因为其具有良好的压电性能、机电耦合特性、高居里温度点等众多优异性能，其被广泛应用于压电薄膜，然而随着人类对生态环境的逐渐重视，由于铅对环境具有危害性而被各个国家限制使用，因此急需找寻一种性能相近的环境友好型材料作为替代。掺杂改良后的铌酸钾钠（KNN）基陶瓷由于具有与PZT相比拟的物理性能，被认为是最有可能取代PZT材料的候选材料之一。因此，本专利用固相反应法制备了KNN基陶瓷，以此为靶材，利用LMBE法制备超薄压电薄膜。
发明内容
技术问题：铅基材料污染环境以及超薄压电薄膜制备过程中合格率不高。
为了解决上述技术问题，本发明所采取的技术方案如下：
一种超薄铌酸钾钠基柔性压电薄膜材料，其化学分子式为：(1-x)(K0.48Na0.48Li0.02)Nb0.8Ta0.2O3-xLn(Zr1-y Ti y )O3 (KNN-LT)，其中Ln为Ca，Ba及Sr中的一种或多种；x和y 为摩尔数，0<x<0.1，0≤y≤1。
本发明还提供一种超薄铌酸钾钠基柔性压电薄膜材料的制备方法，该方法包括Sr3Al2O6靶材制备、KNN-LT靶材制备以及KNN-NBT薄膜制备。
A. Sr3Al2O6靶材制备：利用传统固相反应法制备Sr3Al2O6靶材，包括以下步骤：
（1）根据Sr3Al2O6化学分子式计算出SrCO3和Al2O3等高纯(>99%)原料的重量，根据计算结果精确依次称取各高纯原料。
（2）将步骤（1）称好的原料加入到尼龙球磨罐，并加入直径3～6mm的氧化锆球和无水乙醇，其中原料、氧化锆球及无水乙醇的质量比为1：2：1。将装有原料、氧化锆球及无水乙醇的球磨罐放入球磨机，球磨6～8h得到浆料，将浆料快速烘干得到混合均匀的粉体。
（3）将步骤（2）得到的粉体放入带盖的氧化铝坩埚中，以3～5oC/min的升温速率升温到900～950oC，保温3～6h，得到反应充分的粉体。
（4）将步骤（3）得到的粉体重复步骤（2），得到较细的粉体，
粉体中加入5～10%（质量分数）的浓度为5%（质量分数）的聚乙烯醇，在玛瑙研钵中研磨至过80目筛网；在200～300MPa压力下压制层圆形坯体，在马弗炉中以1oC/min的升温速率升温到500～550oC排胶。
（5）将排胶片放入带盖的氧化铝坩埚中，以3～5oC/min的升温速率升温到1300～1400oC，保温8～12h，得到Sr3Al2O6靶材。
B．KNN-LT靶材制备：利用传统固相反应法制备KNN-LT靶材，包括以下步骤：
（1）根据KNN-LT化学分子式计算出K2CO3, Na2CO3, Nb2O5, Ta2O5,, Li2CO3, SrCO3或BaCO3或CaCO3，TiO2, ZrO2等高纯(>99%)原料的重量，根据计算结果精确依次称取各高纯原料。为了防止Li，Na，K等的挥发导致化学组分的偏离，称取原料时需要将K2CO3, Na2CO3,Li2CO3过量5～10%的摩尔数。
（2）混料过程与Sr3Al2O6靶材制备的步骤（2）相同。
（3）将步骤（2）得到的粉体放入带盖的氧化铝坩埚中，以3～5oC/min的升温速率升温到800～850oC，保温3～6h，得到反应充分的粉体。
（4）造粒，成型及排胶过程与Sr3Al2O6靶材制备的步骤（4）相同。
（5）将排胶片放入带盖的氧化铝坩埚中，以3～5oC/min的升温速率升温到1050～1150oC，保温3～6h，得到KNN-LT靶材。
C. 制备KNN-LT柔性薄膜，采用激光分子束外延法（Laser Molecular BeamEpitaxy，LMBE）制KNN-LT柔性薄膜备，包括以下步骤：
（1）将SrTiO3基片依次浸入在丙酮，去离子水，乙醇中超声清洗，然后用N2气吹干，将基本在氧压为5×10-6torr，温度为900-1000oC的环境中预处理20～30min，将预处理的基片放入沉积室的基片托上。
（2）将Sr3Al2O6靶材放入沉积室的靶材托上，将真空室抽真空，将衬底加热到700-750oC；通入氧气，使氧分压在1×10-6torr。待温度和氧分压稳定后，将激光能量调节到1.2～1.3J/cm2开始生长薄膜。
（3）Sr3Al2O6薄膜生长到10-20nm后，停止生长，关闭气路和真空泵，取出Sr3Al2O6靶材，将KNN-LT靶材放入沉积室的靶材托上，
（4）将真空室抽真空，将衬底加热到700-750oC；通入氧气，使氧分压在1×10-5torr。温度和氧分压稳定后，将激光能量调节到1.2～1.3J/cm2开始生长单层膜。
（5）KNN-LT单层薄膜生长完成后，关闭气路和真空泵，取出薄膜，将上述薄膜附着在聚二甲基硅烷（PDMS）表面。将上述样品放入室温的水中将Sr3Al2O6溶解，从而将KNN-LT单层薄膜与SrTiO3(001)基片分离开。将KNN-LT附着的PDMS转移到目标柔性基片上，在70oC的水中溶解PDMS，从而获得超薄柔性薄膜。
有益效果：本发明使用环境友好型无铅原料，制备的KNN-LT靶材压电性能优良且稳定，可满足正常使用需求。使用Sr3Al2O6作为牺牲层、用LMBE法制备的柔性薄膜表面平整、组分精确、柔性好、厚度薄可接近临界厚度及制备合格率高。
附图说明
图1为KNN-LT-1薄膜从SrTiO3基底转移到目标基础底工艺图。
图2为KNN-LT-1薄膜的XRD图。
图3为KNN-LT-1薄膜的介电温谱图。
图4为KNN-LT-1薄膜的电滞回线。
具体实施方式
实施例一
一种超薄铌酸钾钠基柔性压电薄膜材料，其化学式为：0.96(K0.48Na0.48Li0.02)Nb0.8Ta0.2O3-0.04 Ca(Zr0.06 Ti0.94)O3 (KNN-LT-1)。用Sr3Al2O6做牺牲层、用LMBE制备，具体过程如下：
A. Sr3Al2O6靶材制备：利用传统固相反应法制备Sr3Al2O6靶材，包括以下步骤：
（1）根据Sr3Al2O6化学分子式计算出SrCO3和Al2O3等高纯(>99%)原料的重量，根据计算结果精确依次称取各高纯原料。
（2）将步骤（1）称好的原料加入到尼龙球磨罐，并加入直径3～6mm的氧化锆球和无水乙醇，其中原料、氧化锆球及无水乙醇的质量比为1：2：1。将装有原料、氧化锆球及无水乙醇的球磨罐放入球磨机，球磨6h得到浆料，将浆料快速烘干得到混合均匀的粉体。
（3）将步骤（2）得到的粉体放入带盖的氧化铝坩埚中，以3～5oC/min的升温速率升温到950oC，保温4h，得到反应充分的粉体。
（4）将步骤（3）得到的粉体重复步骤（2），得到较细的粉体，
粉体中加入7%（质量分数）的浓度为5%（质量分数）的聚乙烯醇，在玛瑙研钵中研磨至过80目筛网；在200MPa压力下压制层圆形坯体，在马弗炉中以1oC/min的升温速率升温到550oC排胶。
（5）将排胶片放入带盖的氧化铝坩埚中，以5oC/min的升温速率升温到1350oC，保温10h，得到Sr3Al2O6靶材。
B．KNN-LT-1靶材制备：利用传统固相反应法制备KNN-LT-1靶材，包括以下步骤：
（1）根据KNN-LT-1化学分子式计算出K2CO3, Na2CO3, Nb2O5, Ta2O5,, Li2CO3, CaCO3，TiO2, ZrO2等高纯(>99%)原料的重量，根据计算结果精确依次称取各高纯原料。为了防止Li，Na，K等的挥发导致化学组分的偏离，称取原料时需要将K2CO3, Na2CO3, Li2CO3过量7%的摩尔数。
（2）混料过程与Sr3Al2O6靶材制备的步骤（2）相同。
（3）将步骤（2）得到的粉体放入带盖的氧化铝坩埚中，以5oC/min的升温速率升温到850oC，保温4，得到反应充分的粉体。
（4）造粒，成型及排胶过程与Sr3Al2O6靶材制备的步骤（4）相同。
（5）将排胶片放入带盖的氧化铝坩埚中，以5oC/min的升温速率升温到1150oC，保温3h，得到KNN-LT-1靶材。
C. 制备KNN-LT-1柔性薄膜，采用激光分子束外延法（Laser Molecular BeamEpitaxy，LMBE）制KNN-LT-1柔性薄膜备，包括以下步骤：
（1）将SrTiO3基片依次浸入在丙酮，去离子水，乙醇中超声清洗，然后用N2气吹干，将基本在氧压为5×10-6torr，温度为900oC的环境中预处理20min，将预处理的基片放入沉积室的基片托上。
（2）将Sr3Al2O6靶材放入沉积室的靶材托上，将真空室抽真空，将衬底加热到750oC；通入氧气，使氧分压在1×10-6torr。待温度和氧分压稳定后，将激光能量调节到1.3J/cm2开始生长薄膜。
（3）Sr3Al2O6薄膜生长到20nm后，停止生长，关闭气路和真空泵，取出Sr3Al2O6靶材，将KNN-LT-1靶材放入沉积室的靶材托上，
（4）将真空室抽真空，将衬底加热到750oC；通入氧气，使氧分压在1×10-5torr。温度和氧分压稳定后，将激光能量调节到0.4J/cm2开始生长单层膜。
（5）KNN-LT-1单层薄膜生长完成后，关闭气路和真空泵，取出薄膜，将上述薄膜附着在聚二甲基硅氧烷（PDMS）表面。将上述样品放入室温的水中将Sr3Al2O6溶解，从而将KNN-LT-1单层薄膜与SrTiO3(001)基片分离开。将KNN-LT-1附着的PDMS转移到目标柔性基片上，在70oC的水中溶解PDMS，从而获得超薄柔性薄膜，如图1所示。
实施例二
一种超薄铌酸钾钠基柔性压电薄膜材料，其化学式为： 0.95(K0.48Na0.48Li0.02)Nb0.8Ta0.2O3-0.05(Ca0.5 Sr0.5)TiO3，制备方法与实施例一相同。
实施例三
一种超薄铌酸钾钠基柔性压电薄膜材料，其化学式为：0.94(K0.48Na0.48Li0.02)Nb0.8Ta0.2O3-0.06(Ca0.5 Ba0.5)ZrO3，制备方法与实施例二相同。
本发明制备的超薄铌酸钾钠基柔性压电薄膜性能稳定，成分均匀，厚度可控。图2展示了实施例一制备的KNN-LT-1薄膜的XRD，从图中可以看出，薄膜为结晶度良好的KNN基压电薄膜，对实施例二和实施例三做了相同的实验，结果与实施例一相似，这里不再叙述。图3展示了实施例一制备的KNN-LT-1薄膜的介电温谱图，居里温度点Tc大约为400oC左右，介电常数为600左右，对实施例二和实施例三做了相同的实验，结果与实施例一相似，这里不再叙述。图4展示了实施例一制备的KNN-LT-1薄膜的电滞回线，从图中可以看出KNN-LT-1薄膜具有良好的铁电性能，剩余极化强度Pr为20µC/cm2，矫顽场Ec为60kV/cm，对实施例二和实施例三做了相同的实验，结果与实施例一相似，这里不再叙述。对实施例一进行测试，其压电常数大约为130pm/V，在对实施例二和实施例三做了相同的实验，结果与实施例一相似，这里不再叙述。

Claims (2)

1.一种超薄铌酸钾钠基柔性压电薄膜材料，其特征在于：其化学分子式为：(1-x)(K0.48Na0.48Li0.02) Nb0.8Ta0.2O3-xLn(Zr1-y Ti y ) O3 (KNN-LT)，其中Ln为Ca，Ba及Sr中的一种或多种；x和y 为摩尔数，0<x<0.1，0≤y≤1。
2.根据权利要求1所述的超薄铌酸钾钠基柔性压电薄膜材料的制备方法，其特征在于：该方法包括Sr3Al2O6靶材制备、KNN-LT靶材制备以及KNN-NBT薄膜制备；
A. Sr3Al2O6靶材制备：利用传统固相反应法制备Sr3Al2O6靶材，包括以下步骤：
（1）根据Sr3Al2O6化学分子式计算出SrCO3和Al2O3等高纯(>99%)原料的重量，根据计算结果精确依次称取各高纯原料；
（2）将步骤（1）称好的原料加入到尼龙球磨罐，并加入直径3～6mm的氧化锆球和无水乙醇，其中原料、氧化锆球及无水乙醇的质量比为1：2：1,将装有原料、氧化锆球及无水乙醇的球磨罐放入球磨机，球磨6～8h得到浆料，将浆料快速烘干得到混合均匀的粉体；
（3）将步骤（2）得到的粉体放入带盖的氧化铝坩埚中，以3～5oC/min的升温速率升温到900～950oC，保温3～6h，得到反应充分的粉体；
（4）将步骤（3）得到的粉体重复步骤（2），得到较细的粉体，
粉体中加入5～10%（质量分数）的浓度为5%（质量分数）的聚乙烯醇，在玛瑙研钵中研磨至过80目筛网；在200～300MPa压力下压制层圆形坯体，在马弗炉中以1oC/min的升温速率升温到500～550 oC排胶；
（5）将排胶片放入带盖的氧化铝坩埚中，以3～5oC/min的升温速率升温到1300～1400oC，保温8～12h，得到Sr3Al2O6靶材；
B．KNN-LT靶材制备：利用传统固相反应法制备KNN-LT靶材，包括以下步骤：
（1）根据KNN-LT化学分子式计算出K2CO3, Na2CO3, Nb2O5, Ta2O5,, Li2CO3, SrCO3或BaCO3或CaCO3，TiO2, ZrO2等高纯(>99%)原料的重量，根据计算结果精确依次称取各高纯原料,为了防止Li，Na，K等的挥发导致化学组分的偏离，称取原料时需要将K2CO3, Na2CO3,Li2CO3过量5～10%的摩尔数；
（2）混料过程与Sr3Al2O6靶材制备的步骤（2）相同；
（3）将步骤（2）得到的粉体放入带盖的氧化铝坩埚中，以3～5oC/min的升温速率升温到800～850oC，保温3～6h，得到反应充分的粉体；
（4）造粒，成型及排胶过程与Sr3Al2O6靶材制备的步骤（4）相同；
（5）将排胶片放入带盖的氧化铝坩埚中，以3～5oC/min的升温速率升温到1050～1150oC，保温3～6h，得到KNN-LT靶材；
C. 制备KNN-LT柔性薄膜，采用激光分子束外延法（Laser Molecular Beam Epitaxy，LMBE）制KNN-LT柔性薄膜备，包括以下步骤：
（1）将SrTiO3基片依次浸入在丙酮，去离子水，乙醇中超声清洗，然后用N2气吹干，将基本在氧压为5×10-6torr，温度为900～1000oC的环境中预处理20～30min，将预处理的基片放入沉积室的基片托上；
（2）将Sr3Al2O6靶材放入沉积室的靶材托上，将真空室抽真空，将衬底加热到700-750oC；通入氧气，使氧分压在1×10-6torr,待温度和氧分压稳定后，将激光能量调节到0.3～0.4J/cm2开始生长薄膜；
（3）Sr3Al2O6薄膜生长到10～20nm后，停止生长，关闭气路和真空泵，取出Sr3Al2O6靶材，将KNN-LT靶材放入沉积室的靶材托上；
（4）将真空室抽真空，将衬底加热到700～750oC；通入氧气，使氧分压在1×10-5torr；
温度和氧分压稳定后，将激光能量调节到1.2～1.3J/cm2开始生长单层膜；
（5）KNN-LT单层薄膜生长完成后，关闭气路和真空泵，取出薄膜，将上述薄膜附着在聚二甲基硅氧烷（PDMS）表面,将上述样品放入室温的水中将Sr3Al2O6溶解，从而将KNN-LT单层薄膜与SrTiO3(001)基片分离开,将KNN-LT附着的PDMS转移到目标柔性基片上，在70oC的水中溶解PDMS，从而获得超薄柔性薄膜。
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