CN114436641A - 一种磁控溅射陶瓷靶材及制备方法 - Google Patents

一种磁控溅射陶瓷靶材及制备方法 Download PDF

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CN114436641A
CN114436641A CN202210197348.9A CN202210197348A CN114436641A CN 114436641 A CN114436641 A CN 114436641A CN 202210197348 A CN202210197348 A CN 202210197348A CN 114436641 A CN114436641 A CN 114436641A
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zinc
sintering
tungstate
bismuthate
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CN114436641B (zh
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许积文
余晨旭
杨玲
王�华
周贤界
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Guilin University of Electronic Technology
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Abstract

本发明公开了一种磁控溅射陶瓷靶材及制备方法，所述陶瓷靶材由氧化锌、掺杂物和助烧物组成，所述掺杂物含量占比为0.7‑2.5wt%，所述助烧物含量占比为0.08‑0.15wt%；所述掺杂物的组成为钨酸锌和/或钼酸锌，当掺杂物为钨酸锌和钼酸锌的混合物时，其中钨酸锌的占比为30‑70wt%；所述助烧物为硼酸锌、硅酸锌和铋酸锌的混合物，其中硼酸锌、硅酸锌和铋酸锌的占比分别为20‑30wt%、40‑60wt%和20‑30wt%。采用本发明提供的陶瓷靶材进行磁控溅射镀膜，可以获得高载流子迁移率的透明导电薄膜。

Description

一种磁控溅射陶瓷靶材及制备方法
技术领域
本发明涉及材料技术领域，具体涉及一种磁控溅射陶瓷靶材及制备方法。
背景技术
在薄膜太阳能电池中，需要使用到具有透明和导电功能的透明导电氧化物（TCO）薄膜作为透明电极。被广泛使用的TCO薄膜材料是氧化铟基陶瓷，如氧化铟锡（ITO）薄膜材料，它具有优异的导电性和透光性。但是，ITO材料使用贵金属铟，不仅材料成本高，而且价格波动大，不利于薄膜太阳能电池成本降低和价格稳定。可以替代ITO薄膜材料的材料较多，如氧化锡基、氧化锌基、石墨烯、纳米银等。在这些潜在的替代材料中，氧化锌基TCO薄膜具有综合的光电性能、材料成本、与ITO薄膜工艺兼容。
制备透明导电氧化物（TCO）薄膜的方法有多种，如电子束热蒸镀，磁控溅射，脉冲激光沉积，喷雾热解，化学气相沉积等，各种制备工艺对靶材的要求有所不同。
为了提高氧化锌基陶瓷靶材的导电性，通常在氧化锌中加入可以形成自由电子的掺杂元素，如Al、Ga、In等，这些有掺杂元素存在的薄膜，载流子浓度高，在红外波段的透光率低，不利于太阳能电池对红外波段能量的转换。因此，需要降低载流子浓度，提高红外波段的透光率。根据公式σ=μne（μ是载流子迁移率，n是载流子浓度，e是电子电量），为了保证TCO薄膜良好的导电性，降低载流子浓度的同时，需要提高载流子的迁移率。
发明内容
本发明提供了一种用于磁控溅射工艺的氧化锌基陶瓷靶材及制备方法，通过在氧化锌基体中掺杂钨、钼而制备的陶瓷靶材，进行磁控溅射镀膜，可以获得高载流子迁移率的透明导电薄膜。同时，为解决陶瓷靶材由于钨、钼的氧化物在烧结过程中容易分解、挥发而导致烧结密度难以提高和成分不均匀，进而引起镀膜过程中陶瓷靶材表面易中毒影响镀膜的连续性，以及薄膜组分不均匀导致光电性能不一致的问题，通过加入微量的硼酸锌、硅酸锌和铋酸锌的混合物作为助烧物，降低烧结温度，尽量避免掺杂组份的分解、挥发。烧结气氛为氧气气氛，也可有效抑制烧结过程中的钨、钼、硼、铋的挥发。
本发明提供的磁控溅射陶瓷靶材，包括氧化锌、掺杂物、助烧物，所述掺杂物为钨酸锌和/或钼酸锌，掺杂物含量与总量比为0.7-2.5wt%，当掺杂物为钨酸锌和钼酸锌的混合物时，其钨酸锌的质量比为30-70wt%。所述助烧物为硼酸锌、硅酸锌和铋酸锌的混合物，助烧物含量与总量比为0.08-0.15wt%，其中硼酸锌、硅酸锌和铋酸锌的质量比分别为20-30wt%、40-60wt%、20-30wt%。
本发明提供的磁控溅射陶瓷靶材，其制备方法包括以下步骤：
（1）按照配比称取各种粉体原料、分散剂、去离子和粘接剂，其中掺杂物采用钨酸锌、钼酸锌粉体，助烧物采用硼酸锌、硅酸锌、铋酸锌粉体。
（2）将粉体原料与去离子水、分散剂混合，再砂磨混合与粉碎。
（3）在砂磨浆料中加入聚乙烯醇粘接剂进行喷雾造粒。
（4）将造粒粉体放入模具中进行模压成型，再用冷等静压进行强化处理或直接进行冷等静压。
（5）将素坯先低温烧结去掉粘接剂，再高温气氛烧结为致密陶瓷体.
（6）烧结温度升至600℃时通入氧气，降温到900℃时停止。
（7）将陶瓷体机加工，获得磁控溅射陶瓷靶材。
本发明的技术特点和有益效果：
（1）采用不易挥发的钨酸锌、钼酸锌粉体作为原材料，在氧化锌中掺杂钨、钼两种元素，达到提高靶材载流子迁移率的目的。
（2）通过加入微量的硼酸锌、硅酸锌和铋酸锌的混合物作为助烧物，降低靶材烧结温度，尽量避免掺杂组份的分解、挥发。同时，采用氧气气氛烧结，也可有效抑制烧结过程中的钨、钼、硼、铋的挥发。
（3）钨酸锌、钼酸锌作为掺杂原材料，烧结过程中钨酸锌、钼酸锌与主材氧化锌反应时钨、钼占据氧化锌的锌晶格位置，留下相同材质的氧化锌，没有引起杂质污染。同时，避免易挥发的氧化钨、氧化钼为原料时存在烧结挥发，影响陶瓷体的密度、内部与近表面位置组分一致性问题。另外，硼酸锌、硅酸锌和铋酸锌也具有类似作用。
附图说明
图1展示了实施例1的陶瓷靶材的微观结构；
图2展示了对比例2的陶瓷靶材的微观结构。
具体实施方式
通过下面给出的实施例和对比例，可以充分理解本发明的技术方案，以及相对于现有技术展现出的有益效果。
实施例1：
粉体投料的总质量为10kg，氧化锌粒度为120nm，钨酸锌粒度为0.40μm，硼酸锌粒度为1.0μm，硅酸锌粒度为0.80μm，铋酸锌粒度0.72μm。钨酸锌含量为0.7wt%，硼酸锌、硅酸锌和铋酸锌的含量为0.08wt%（其中，硼酸锌20wt%，铋酸锌20wt%，硅酸锌60wt%）。
用0.6%的聚丙稀酸铵为分散剂，加入纯水控制浆料固含量为53%，高速分散后进行砂磨3h，其激光粒度（D50）为0.32μm。加入1.4%的聚乙烯醇粘接剂后喷雾造粒，其造粒粉体的松装密度为1.2g/cm3。用200×300mm2的模具在60MPa模压再用180MPa冷等静压强化，其素坯的相对密度为56%。素坯放入烧结炉，先以1℃/min升温到550℃，保温10h脱脂，然后以0.5℃/min升温到1400℃，保温0.5h，以1.2℃/min降温到1250℃，保温10h；600℃通入氧气，氧气流量为20L/h，降温到900℃时停止通入氧气。降温到室温后，取出靶材进行线切割、平面磨、表面抛光获得可磁控溅射的靶材。密度用阿基米德排水法检测，靶材的相对密度为98.9%，靶材的微结构如图1所示。
将机加工的平面靶材切割成直径为60mm靶材并绑定，在磁控溅射镀膜机中进行镀膜评估，基材为0.55mm厚的康宁玻璃，直流电源，工作气体为氩气，反应气体为氧气，在优化工艺条件下制备的薄膜的电子迁移率为34.1cm2/V·s。
实施例2：
总的粉体投料10kg，氧化锌为120nm，钼酸锌0.51μm、硼酸锌1.0μm、硅酸锌0.80μm、铋酸锌0.72μm。钼酸锌含量为2.5wt%，硼酸锌、硅酸锌和铋酸锌的含量为0.08wt%（其中，硼酸锌30wt%，铋酸锌30wt%，硅酸锌40wt%）。
用0.6%的聚丙稀酸铵为分散剂，加入纯水控制浆料固含量为50%，高速分散后进行砂磨3.5h，其激光粒度（D50）为0.25μm。加入2.0%的聚乙烯醇粘接剂后喷雾造粒，其造粒粉体的松装密度为1.5g/cm3。用200×300mm2的模具在60MPa模压再用260MPa冷等静压强化，其素坯的相对密度为62%。素坯放入烧结炉，先以1℃/min升温到550℃，保温10h脱脂，然后以0.5℃/min升温到1350℃，保温1h，以1.2℃/min降温到1100℃，保温22h；600℃通入氧气，氧气流量为20L/h，降温到900℃时停止通入氧气。降温到室温后，取出靶材进行线切割、平面磨、表面抛光获得可磁控溅射的靶材。密度用阿基米德排水法检测，靶材的相对密度为99.2%。
将机加工的平面靶材切割成直径为60mm靶材并绑定，在磁控溅射镀膜机中进行镀膜评估，基材为0.55mm厚的康宁玻璃，直流电源，工作气体为氩气，反应气体为氧气，在优化的工艺条件下制备的薄膜的电子迁移率为33.6cm2/V·s。
实施例3：
总的粉体投料10kg，氧化锌为120nm，钨酸锌为0.40μm、钼酸锌0.51μm、硼酸锌1.0μm、硅酸锌0.80μm、铋酸锌0.72μm。钨酸锌和钼酸锌的总含量为1.5wt%（钨酸锌30wt%，钼酸锌70wt%），硼酸锌、硅酸锌和铋酸锌的含量为0.1wt%（其中，硼酸锌25wt%，铋酸锌25wt%，硅酸锌50wt%）。
用0.8%的聚丙稀酸铵为分散剂，加入纯水控制浆料固含量为55%，高速分散后进行砂磨4h，其激光粒度（D50）为0.26μm。加入1.5%的聚乙烯醇粘接剂后喷雾造粒，其造粒粉体的松装密度为1.3g/cm3。用200×300mm2的模具在60MPa模压再用220MPa冷等静压强化，其素坯的相对密度为59%。素坯放入烧结炉，先以1℃/min升温到550℃，保温10h脱脂，然后以0.5℃/min升温到1365℃，保温0.7h，以1.5℃/min降温到1150℃，保温20h；600℃通入氧气，氧气流量为10L/h，降温到900℃时停止通入氧气。降温到室温后，取出靶材进行线切割、平面磨、表面抛光获得可磁控溅射的靶材。密度用阿基米德排水法检测，靶材的相对密度为99.1%。
将机加工的平面靶材切割成直径为60mm靶材并绑定，在磁控溅射镀膜机中进行镀膜评估，基材为0.55mm厚的康宁玻璃，直流电源，工作气体为氩气，反应气体为氧气，在优化的工艺条件下制备的薄膜的电子迁移率为40.1cm2/V·s。
实施例4：
总的粉体投料10kg，氧化锌为120nm，钨酸锌为0.40μm、钼酸锌0.51μm、硼酸锌1.0μm、硅酸锌0.80μm、铋酸锌0.72μm。钨酸锌和钼酸锌的总含量为1.5wt%（钨酸锌70wt%，钼酸锌30wt%），硼酸锌、硅酸锌和铋酸锌的含量为0.1wt%（其中，硼酸锌25wt%，铋酸锌25wt%，硅酸锌50wt%）。
用0.5%的聚丙稀酸铵为分散剂，加入纯水控制浆料固含量为50%，高速分散后进行砂磨4h，其激光粒度（D50）为0.27μm。加入1.5%的聚乙烯醇粘接剂后喷雾造粒，其造粒粉体的松装密度为1.3g/cm3。用200×300mm2的模具在60MPa模压再用220MPa冷等静压强化，其素坯的相对密度为58%。素坯放入烧结炉，先以1℃/min升温到550℃，保温10h脱脂，然后以0.5℃/min升温到1365℃，保温0.7h，以1.5℃/min降温到1200℃，保温16h；600℃通入氧气，氧气流量为10L/h，降温到900℃时停止通入氧气。降温到室温后，取出靶材进行线切割、平面磨、表面抛光获得可磁控溅射的靶材。密度用阿基米德排水法检测，靶材的相对密度为99.1%。
将机加工的平面靶材切割成直径为60mm靶材并绑定，在磁控溅射镀膜机中进行镀膜评估，基材为0.55mm厚的康宁玻璃，直流电源，工作气体为氩气，反应气体为氧气，在优化的工艺条件下制备的薄膜的电子迁移率为38.7cm2/V·s。
实施例5：
总的粉体投料10kg，氧化锌为120nm，钨酸锌为0.40μm、钼酸锌0.51μm、硼酸锌1.0μm、硅酸锌0.80μm、铋酸锌0.72μm。钨酸锌和钼酸锌的总含量为1.2wt%（钨酸锌50wt%，钼酸锌50wt%），硼酸锌、硅酸锌和铋酸锌的含量为0.1wt%（其中，硼酸锌25wt%，铋酸锌25wt%，硅酸锌50wt%）。
其制备工艺与实施例4相同。密度用阿基米德排水法检测，靶材的相对密度为99.1%。
将机加工的平面靶材切割成直径为60mm靶材并绑定，在磁控溅射镀膜机中进行镀膜评估，基材为0.55mm厚的康宁玻璃，直流电源，工作气体为氩气，反应气体为氧气，在优化的工艺条件下制备的薄膜的电子迁移率为36.3cm2/V·s。
实施例6：
总的粉体投料10kg，氧化锌为120nm，钨酸锌为0.40μm、钼酸锌0.51μm、硼酸锌1.0μm、硅酸锌0.80μm、铋酸锌0.72μm。钨酸锌和钼酸锌的总含量为1.2wt%（钨酸锌65wt%，钼酸锌35wt%），硼酸锌、硅酸锌和铋酸锌的含量为0.1wt%（其中，硼酸锌25wt%，铋酸锌25wt%，硅酸锌50wt%）。
其制备工艺与实施例4相同。密度用阿基米德排水法检测，靶材的相对密度为99.1%。
将机加工的平面靶材切割成直径为60mm靶材并绑定，在磁控溅射镀膜机中进行镀膜评估，基材为0.55mm厚的康宁玻璃，直流电源，工作气体为氩气，反应气体为氧气，在优化的工艺条件下制备的薄膜的电子迁移率为39.8cm2/V·s。
对比例1：
外购氧化锌/氧化铝成分比为98/2的AZO圆形靶材，直径为60mm。在磁控溅射镀膜机中进行镀膜评估，基材为0.55mm厚的康宁玻璃，直流电源，工作气体为氩气，反应气体为氧气，在优化的工艺条件下制备的薄膜的电子迁移率为10.8cm2/V·s。
对比例2：
外购氧化锌/氧化铝成分比为98/1的AZO圆形靶材，直径为60mm，其微结构如图2所示。在磁控溅射镀膜机中进行镀膜评估，基材为0.55mm厚的康宁玻璃，直流电源，工作气体为氩气，反应气体为氧气，在优化的工艺条件下制备的薄膜的电子迁移率为13.6cm2/V·s。
从以上的实施例和对比例可知，本发明相对于对比例，靶材的电子迁移率和相对密度都获得显著提高，可以降低在溅射过程中的表面节瘤中毒现象，更适合用于太阳能电池的透明电极应用。

Claims (2)

1.一种磁控溅射陶瓷靶材，由氧化锌、掺杂物和助烧物组成，其特征在于，所述掺杂物含量占比为0.7-2.5wt%，所述助烧物含量占比为0.08-0.15wt%；所述掺杂物的组成为钨酸锌和/或钼酸锌，当掺杂物为钨酸锌和钼酸锌的混合物时，其中钨酸锌的占比为30-70wt%；所述助烧物为硼酸锌、硅酸锌和铋酸锌的混合物，其中硼酸锌、硅酸锌和铋酸锌的占比分别为20-30wt%、40-60wt%和20-30wt%。
2.根据权利要求1所述的磁控溅射陶瓷靶材，其特征在于，其制备方法包括以下步骤：
（1）按照配比称取各种粉体原料、分散剂、去离子和粘接剂，其中掺杂物采用钨酸锌、钼酸锌粉体，助烧物采用硼酸锌、硅酸锌、铋酸锌粉体；
（2）将粉体原料与去离子水、分散剂混合，再砂磨混合与粉碎；
（3）在砂磨浆料中加入聚乙烯醇粘接剂进行喷雾造粒；
（4）将造粒粉体放入模具中进行模压成型，再用冷等静压进行强化处理或直接进行冷等静压；
（5）将素坯先低温烧结去掉粘接剂，再高温气氛烧结为致密陶瓷体；
（6）烧结温度升至600℃时通入氧气，降温到900℃时停止。
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