CN111394706B - 一种晶粒尺寸可控ito陶瓷靶材的制备方法 - Google Patents

一种晶粒尺寸可控ito陶瓷靶材的制备方法 Download PDF

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CN111394706B
CN111394706B CN202010150796.4A CN202010150796A CN111394706B CN 111394706 B CN111394706 B CN 111394706B CN 202010150796 A CN202010150796 A CN 202010150796A CN 111394706 B CN111394706 B CN 111394706B
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temperature
powder
sintering
degreasing
ito
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CN111394706A (zh
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何季麟
孙本双
舒永春
刘洋
陈杰
曾学云
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Zhengzhou University
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Zhengzhou University
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    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/786—Micrometer sized grains, i.e. from 1 to 100 micron

Abstract

一种晶粒尺寸可控ITO陶瓷靶材的制备方法，包括：将质量份数为90～97的In2O3粉体和质量份数为10～3的SnO2粉体，与去离子水、稀释剂、粘结剂和高分子材料用砂磨机球磨混合，得到固含量在70～80％之间、粘度在120～300mpa.s之间的ITO陶瓷浆料，且混合粉体的平均粒径D50控制在100～300nm；ITO陶瓷浆料经压力注浆成形，得到相对密度为58～62％的ITO陶瓷生坯体；将ITO陶瓷生坯体放入脱脂烧结一体化炉，加热至脱脂温度700～800℃，将ITO陶瓷靶材在常压氧气氛中进行脱脂处理，时间设定为12～36小时；从脱脂温度升温到第一烧结温度1600～1650℃，常压氧气氛保温0～60min，随即降低到第二烧结温度1500～1540℃，常压氧气氛保温12～36小时，最终得到ITO陶瓷靶材。

Description

一种晶粒尺寸可控ITO陶瓷靶材的制备方法
技术领域
本申请属于陶瓷靶材制备技术领域，具体涉及一种晶粒尺寸可控ITO陶瓷靶材的制备方法。
背景技术
ITO陶瓷靶材是制备导电玻璃上透明导电薄膜(TCO)的主要原材料。ITO陶瓷靶材通过溅射在玻璃基板上形成一层透明的导电薄膜，该薄膜经过处理后便形成常见的透明电极。与其他氧化物薄膜相比，ITO(Indium Tin Oxide)导电薄膜的性能最为优良，其主要原因是其具有良好的导电性(电阻率10-4Ω·cm)，透光性(透过率>85％)；高紫外线吸收率(吸收率>85％)；红外线单向穿透性(反射率>80％)。
ITO陶瓷靶材性能的好坏直接决定着ITO导电玻璃的质量、生产效率、成品率的关键。一般来讲，高性能ITO陶瓷靶材应具备以下性能：高纯度(>99.99％)、高密度(相对密度>99.5％)、低电阻率(<0.14mΩ·cm)、大尺寸和相结构均匀性。尤其是相结构均匀性，包括二次相(In4Sn3O12相)分布含量及均匀性，对磁控溅射制备ITO薄膜工艺过程及性能有着及其重要的影响。ITO陶瓷靶材的晶粒细小均匀，可以降低靶材溅射过程中的结瘤现象，可以提高靶材的利用率；同时可以提高ITO薄膜的光电性能的稳定性。
目前常用制备ITO陶瓷靶材的烧结方法是采用脱脂和烧结分开进行的工艺。针对该烧结工艺，如果最高烧结温度低于1540℃时，ITO陶瓷靶材无法完全致密化，其内部微观组织仍然会有很多孔洞；而其最高烧结温度高于1600℃时，又会出现晶粒粗大且均匀性差等缺陷。
发明内容
为了至少解决以上提到的现有技术存在的技术问题之一，本申请实施例公开了一种晶粒尺寸可控ITO陶瓷靶材的制备方法，该制备方法包括以下步骤：
将质量份数为90～97的In2O3粉体和质量份数为10～3的SnO2粉体，与去离子水、稀释剂、粘结剂和高分子材料用砂磨机球磨混合，得到固含量在70～80％之间、粘度在120～300mpa.s之间的ITO陶瓷浆料，且ITO陶瓷浆料中混合粉体的平均粒径D50控制在200～300nm；
ITO陶瓷浆料经压力注浆成形，得到相对密度为58～62％的ITO陶瓷生坯体；
ITO陶瓷生坯体经一体化脱脂烧结处理，得到ITO陶瓷靶材；其中，所述一体化脱脂烧结处理具体包括：
将ITO陶瓷生坯体放入脱脂烧结一体化炉；
将脱脂烧结一体化炉加热至脱脂温度700～800℃，将ITO陶瓷靶材在常压氧气氛中进行脱脂处理，脱脂时间设定为12～36小时；
将脱脂烧结一体化炉从脱脂温度升温到第一烧结温度1600～1650℃；
升温到第一烧结温度后，在第一烧结温度下保温0～60min，随即开始将脱脂烧结一体化炉从第一烧结温度降低到第二烧结温度1500～1540℃，将ITO靶材在第二烧结温度、常压氧气氛中进行烧结处理，保温12～36小时，最终得到ITO陶瓷靶材。
一些实施例公开的晶粒尺寸可控ITO陶瓷靶材的制备方法，In2O3粉体和SnO2粉体的质量份数为90和10。
一些实施例公开的晶粒尺寸可控ITO陶瓷靶材的制备方法，In2O3粉体和SnO2粉体的质量份数为95和5。
一些实施例公开的晶粒尺寸可控ITO陶瓷靶材的制备方法，In2O3粉体和SnO2粉体的质量份数为93和7。
一些实施例公开的晶粒尺寸可控ITO陶瓷靶材的制备方法，In2O3粉体的一次颗粒粒径分布范围为80～200nm，SnO2粉体的一次颗粒粒径分布范围为80～200nm。
一些实施例公开的晶粒尺寸可控ITO陶瓷靶材的制备方法，稀释剂包括聚丙烯酸类或聚羧酸类稀释剂，粘结剂包括阿拉伯树胶、聚乙烯醇或丙烯酸树脂，高分子材料包括聚丙烯酰胺。
一些实施例公开的晶粒尺寸可控ITO陶瓷靶材的制备方法，In2O3粉体和SnO2粉体，与去离子水、稀释剂、粘结剂和高分子材料在砂磨机中真空负压条件下球磨混合，负压压力不大于9Pa。
一些实施例公开的晶粒尺寸可控ITO陶瓷靶材的制备方法，从室温到脱脂温度的升温速率设置为1～3℃/min。
一些实施例公开的晶粒尺寸可控ITO陶瓷靶材的制备方法，从脱脂温度到第一烧结温度的升温速率设定为2～5℃/min。
一些实施例公开的晶粒尺寸可控ITO陶瓷靶材的制备方法，从第一烧结温度到第二烧结温度的降温速率设定为8～16℃/min。
本申请实施例公开的晶粒尺寸可控ITO陶瓷靶材的制备方法，从粉体一次粒径分布、混合粉体球磨分散粒径分布、成形工艺及烧结工艺协同优化组合，ITO陶瓷靶材晶体结构等方面进行了创新研究，制备得到了晶粒尺寸可控的ITO陶瓷靶材，拥有优异的电学和力学等性能，利于制备高质量ITO薄膜。工艺操作简便，生坯烧结性好，便于制备各种尺寸的ITO陶瓷靶材，且ITO陶瓷靶材密度高、电阻率低、晶粒细小且粒度分布均匀，其相对密度可达99.7％，电阻率低至0.13mΩ·cm，晶粒尺寸可控，其数值可低至3～5μm，降低的烧结温度可以相应的降低生产成本，延长设备使用寿命，适用于工业化生产。
附图说明
图1为实施例1中ITO陶瓷靶材的扫描电镜图
图2为实施例2中ITO陶瓷靶材的扫描电镜图
图3为实施例3中ITO陶瓷靶材的扫描电镜图
图4为比较例1中ITO陶瓷靶材的扫描电镜图
图5为比较例2中ITO陶瓷靶材的扫描电镜图
图6为比较例3中ITO陶瓷靶材的扫描电镜图
具体实施方式
在这里专用的词“实施例”，作为“示例性”所说明的任何实施例不必解释为优于或好于其它实施例。本申请实施例中性能指标测试，除非特别说明，采用本领域常规试验方法。应理解，本申请中所述的术语仅仅是为描述特别的实施方式，并非用于限制本申请公开的内容。
除非另有说明，否则本文使用的技术和科学术语具有本申请所属技术领域的普通技术人员通常理解的相同含义；作为本申请中其它未特别注明的试验方法和技术手段均指本领域内普通技术人员通常采用的实验方法和技术手段。
本公开所用的术语“基本”和“大约”用于描述小的波动。例如，它们可以是指小于或等于±5％，如小于或等于±2％，如小于或等于±1％，如小于或等于±0.5％，如小于或等于±0.2％，如小于或等于±0.1％，如小于或等于±0.05％。浓度、量和其它数值数据在本文中可以以范围格式表示或呈现。这样的范围格式仅为方便和简要起见使用，因此应灵活解释为不仅包括作为该范围的界限明确列举的数值，还包括该范围内包含的所有独立的数值或子范围。例如，“1～5％”的数值范围应被解释为不仅包括1％至5％的明确列举的值，还包括在所示范围内的独立值和子范围。因此，在这一数值范围中包括独立值，如2％、3.5％和4％，和子范围，如1％～3％、2％～4％和3％～5％等。这一原理同样适用于仅列举一个数值的范围。此外，无论该范围的宽度或所述特征如何，这样的解释都适用。
在本公开，包括权利要求书中，所有连接词，如“包含”、“包括”、“带有”、“具有”、“含有”、“涉及”、“容纳”等被理解为是开放性的，即是指“包括但不限于”。只有连接词“由……构成”和“由……组成”是封闭连接词。
为了更好的说明本申请内容，在下文的具体实施例中给出了众多的具体细节。本领域技术人员应当理解，没有某些具体细节，本申请同样可以实施。在实施例中，对于本领域技术人员熟知的一些方法、手段、仪器、设备等未作详细描述，以便凸显本申请的主旨。在不冲突的前提下，本申请实施例公开的技术特征可以任意组合，得到的技术方案属于本申请实施例公开的内容。
在一些实施方式中，晶粒尺寸可控ITO陶瓷靶材的制备方法包括以下步骤：
料浆制备步骤，即将质量份数为90～97的In2O3粉体和质量份数为10～3的SnO2粉体，与去离子水、稀释剂、粘结剂和高分子材料在砂磨机中球磨混合，得到固含量在70～80％之间、粘度在120～300mpa.s之间的ITO陶瓷浆料；采用砂磨机分散后的ITO陶瓷浆料中混合粉体的平均粒径D50控制在200～300nm；本申请述及的混合粉体是指包括In2O3粉体和SnO2粉体的粉体混合物；控制混合粉体的粒径对产物的性能影响很大，尤其是混合粉体的平均粒径与ITO陶瓷靶材的晶粒尺寸控制密切相关，平均粒径D50控制在200～300nm之间，能够得到理想的结果；
坯体成型步骤，即ITO陶瓷浆料经压力注浆成形，得到ITO陶瓷生坯体，且该生坯体的相对密度不低于62％；ITO陶瓷靶材生坯体的相对密度是控制其最终产物ITO靶材致密化程度的重要参数之一，生坯体相对密度控制在62％以上可得到致密化程度高的ITO陶瓷靶材；
坯体一体化脱脂烧结步骤，即ITO陶瓷生坯体经一体化脱脂烧结处理，得到ITO陶瓷靶材；其中，一体化脱脂烧结处理具体包括：将ITO陶瓷生坯体放入脱脂烧结一体化炉；将脱脂烧结一体化炉加热至脱脂温度700～800℃，将ITO陶瓷靶材在常压氧气氛中进行脱脂处理，脱脂时间设定为12～36小时；脱脂过程结束后将脱脂烧结一体化炉从脱脂温度升温到第一烧结温度1600～1650℃；升温到第一烧结温度后，在该烧结温度下保温0～60min，随即从第一烧结温度降低到第二烧结温度1500～1540℃，并在第二烧结温度、常压氧气氛中进行烧结处理，保温12～36小时，最终得到ITO陶瓷靶材。
在一些实施方式中，In2O3粉体的质量分数为90、93、95或97，相对应的，SnO2粉体的质量份数分别为10、7、5或3，以便二者的质量份数之和为100。
在一些实施方式中，In2O3粉体和SnO2粉体的一次颗粒粒径分布范围为80～200nm。
在一些实施方式的浆料制备步骤中，In2O3和SnO2两种氧化物粉体，与去离子水、稀释剂、粘结剂和高分子材料混合，制备成高固含量低粘度的ITO浆料；其中，稀释剂包括聚丙烯酸类或聚羧酸类稀释剂，粘结剂包括阿拉伯树胶、聚乙烯醇或丙烯酸树脂，高分子材料包括聚丙烯酰胺。
在一些实施方式的料浆制备中，In2O3粉体和SnO2粉体，与去离子水、稀释剂、粘结剂和高分子材料在负压环境下采用砂磨机球磨混合，负压压力不大于9Pa。用砂磨机对粉体材料进行混合，一方面可以提高生产效率，另一方面，短时间球磨可以大大减少因氧化锆球研磨掺入到ITO浆料中的锆杂质。作为可选实施方式，可以在砂磨机球磨之前进行预混合球磨，例如在滚筒球磨罐中进行球磨预混合。
通常球磨混合后ITO浆料的固含量对靶材坯体成型有较大影响，实验表明，控制固含量在70～80％之间较为适宜，低于70％的浆料水分含量过高，会导致成形困难，生坯易开裂，而高于80％浆料不易获得，影响料制备工艺的稳定性。
通常，球磨混合后ITO浆料的平均粒径D50控制在200～300nm之间较为适宜；平均粒径低于200nm会导致后续成形出现分层现象而致使ITO生坯质量下降，生坯难以成型，且容易开裂；而高于300nm，则粉体出现粉体微团聚现象，粉体活性不够导致烧结无法完全致密化。
通常球磨混合后ITO浆料的捻度对靶材坯体成型有影响，实验表明，粘度控制在120～300mpa.s之间的ITO陶瓷浆料有利于靶材的成型，粘度低于120的浆料难以获得注浆成型为靶材，高于300的浆料流变性能变差，以注浆难度增大不易成形为靶材坯体；
通常负压下对氧化物料浆进行球磨，一方面可以减少球磨过程中空气和杂质引入到料浆中，另一方面可以省去球磨后对料浆进行真空除泡的工艺，减少设备和时间成本，增加生产效率，本申请实施例公开的负压压力不大于9Pa，即可以达到以上技术效果。
在一些实施方式中，晶粒尺寸可控ITO陶瓷靶材的制备方法包括坯体成形步骤，ITO浆料成形为ITO陶瓷生坯体。
在一些实施方式中，得到的ITO浆料采用压力注浆工艺成形，在特定的压力下，注入模具中，例如石膏模具中，成形得到生坯体。通常ITO生坯体的相对密度控制在58～62％之间。相对密度低于58％，导致烧结后的陶瓷材料无法致密化，且无法有效控制晶粒尺寸，而高于62％，对最后产品烧结效果没有明显提高，反而增加了生产成本。
在一些实施方式中，晶粒尺寸可控ITO陶瓷靶材的制备方法包括一体化脱脂烧结步骤。一体化脱脂烧结步骤通常是指ITO靶材坯体在一定的温度下进行脱脂过程，脱脂过程结束后直接从脱脂温度升温到烧结温度，进行烧结过程，脱脂和烧结过程在同一个装置中连续进行，缩短靶材制备时间，同时避免因为靶材在更换制备设备或环境的过程中造成其结构损伤，影响产品性能。通常ITO靶材的脱脂烧结过程在常压氧气氛的一体化炉中进行，工艺流程简单，避免降低陶瓷表面烧结活性，有利于得到致密化程度高的陶瓷靶材。
作为可选实施方式，通常ITO陶瓷生坯体在一定温度下进行脱脂处理，例如，一些实施例选择的脱脂温度在700～800℃之间。
作为可选实施方式，通常脱脂后的ITO陶瓷生坯体在较高的温度下烧结，得到陶瓷靶材；在一些实施例中，首先将ITO陶瓷靶材坯体升温至第一烧结温度1600～1650℃，随即降温至第二烧结温度1500～1540℃，在第二烧结温度下保温12～36小时。通常烧结过程在常压高纯氧气氛围中进行。
作为可选实施方式，通常脱脂后的ITO陶瓷生坯体在较高的温度下烧结，得到陶瓷靶材；在一些实施例中，首先将ITO陶瓷靶材坯体升温至第一烧结温度1600～1650℃，在第一烧结温度下保持时间不超过60分钟，随即降温至第二烧结温度1500～1540℃，在第二烧结温度下保温12～36小时。通常烧结过程在常压高纯氧气氛围中进行。
在一些实施方式的一体化脱脂烧结步骤中，从室温到脱脂温度的升温速率设置为1～3℃/min。控制脱脂温度的升温速率有利于控制靶材的烧结效果，有利于得到致密度高、电阻率低、晶粒细小均匀的陶瓷靶材，升温速率控制在1～3℃/min属于较为优选的实施方式。
在一些实施方式的一体化脱脂烧结步骤中，从脱脂温度到第一烧结温度的升温速率设定为2～5℃/min。控制第一烧结温度的升温速率有利于控制靶材的烧结效果，有利于得到致密度高、电阻率低、晶粒细小均匀的陶瓷靶材，温速率设定为2～5℃/min属于较为优选的实施方式。
在一些实施方式的一体化脱脂烧结步骤中，从第一烧结温度到第二烧结温度的降温速率设定为8～16℃/min。控制第二烧结温度的降温速率有利于控制靶材的烧结效果，有利于得到致密度高、电阻率低、晶粒细小均匀的陶瓷靶材，降温速率设定为8～16℃/min属于较为优选的实施方式。
以下结合具体实施例，对晶粒尺寸可控ITO陶瓷靶材的制备方法的实施细节进一步描述。
实施例1
本实施例1制备晶粒尺寸可控ITO陶瓷靶材的方法包括：
分别称重450g In2O3粉体和50g SnO2粉体；9g聚丙烯酸、2.5g阿拉伯树胶、9g丙烯酰胺和125g去离子水组成预混液；
将两种氧化物粉体和预混液加入滚筒球磨罐中混合，球磨1小时，然后将浆料转移至砂磨机中高能球磨，将球磨罐的真空度抽至9Pa，得到粉体固体质量含量为80％的ITO浆料，激光粒度仪测得混合粉体平均粒径分布D50为200nm；
将浆料注入石膏模具中，在压力为0.2MPa条件下成形，得到ITO陶瓷生坯体，其相对密度为62％；
将ITO陶瓷生坯体干燥，之后放入脱脂烧结一体炉中，脱脂温度为750℃，时间为24小时，脱脂结束后直接以3℃/min升温速率升至第一烧结温度1640℃，在第一烧结温度下保温30min，然后以16℃/min降温速率降至第二烧结温度1540℃，在第二烧结温度下保温36小时，烧结气氛为常压高纯氧气。
实施例1得到的ITO陶瓷靶材的相对密度为99.7％，电阻率为0.13mΩ·cm，其微观组织形貌如图1所示，陶瓷内部完全致密化且晶粒分布均匀，其晶粒平均尺寸为12.3μm。
实施例2
本实施例2制备晶粒尺寸可控ITO陶瓷靶材的方法包括：
分别称重450g In2O3粉体和50g SnO2粉体；9g聚丙烯酸、2.5g阿拉伯树胶、9g丙烯酰胺和125g去离子水组成预混液；
将两种氧化物粉体和预混液加入滚筒球磨罐中混合，球磨1小时，然后将浆料转移至砂磨机中高能球磨，将球磨罐的真空度抽至9Pa，得到粉体固体质量含量为80％的ITO浆料，激光粒度仪测得混合粉体平均粒径分布D50为200nm；
将浆料注入石膏模具中，在压力为0.2MPa条件下成形，得到ITO陶瓷生坯体，其相对密度为62％；
将ITO陶瓷生坯体干燥，之后放入脱脂烧结一体炉中，脱脂温度为750℃，时间为24小时，脱脂结束后直接以3℃/min升温速率升至第一烧结温度1640℃，然后以16℃/min降温速率降至第二烧结温度1540℃，在T2烧结温度下保温24小时，烧结气氛为常压高纯氧气。
实施例2得到的ITO陶瓷靶材的相对密度为99.5％，电阻率为0.14mΩ·cm，其微观组织形貌如图2所示，完全致密化其晶粒平均尺寸为5.6μm。
实施例3
本实施例3制备晶粒尺寸可控ITO陶瓷靶材的方法包括：
分别称重450g In2O3粉体和50g SnO2粉体；9g聚丙烯酸、2.5g阿拉伯树胶、9g丙烯酰胺和125g去离子水组成预混液；
将两种氧化物粉体和预混液加入滚筒球磨罐中混合，球磨1小时，然后将浆料转移至砂磨机中高能球磨，将球磨罐的真空度抽至9Pa，得到粉体固体质量含量为80％的ITO浆料，激光粒度仪测得混合粉体平均粒径分布D50为200nm；
将浆料注入石膏模具中，在压力为0.2MPa条件下成形，得到ITO陶瓷生坯体，其相对密度为62％；
将ITO陶瓷生坯体干燥，之后放入脱脂烧结一体炉中，脱脂温度为750℃，时间为24小时，脱脂结束后直接以3℃/min升温速率升至第一烧结温度1600℃，然后以16℃/min降温速率降至第二烧结温度1540℃，在第二烧结温度下保温24小时，烧结气氛为常压高纯氧气。
实施例3得到的ITO陶瓷靶材的相对密度为99.6％，电阻率为0.15mΩ·cm，其微观组织形貌如图3所示，完全致密化其晶粒平均尺寸为3.8μm。
比较例1
本比较例1制备晶粒尺寸可控ITO陶瓷靶材的方法包括：
分别称重450g In2O3粉体和50g SnO2粉体；9g聚丙烯酸、2.5g阿拉伯树胶、9g丙烯酰胺和125g去离子水组成预混液；
将氧化物粉体和预混液加入滚筒球磨罐中混合，球磨1小时，然后将浆料转移至砂磨机中高能球磨，将球磨罐的真空度抽至9Pa，得到粉体固体质量含量为80％的ITO浆料，激光粒度仪测得混合粉体平均粒径分布D50为500nm；
将浆料注入石膏模具中，在压力为0.2MPa条件下成形，得到ITO陶瓷生坯体，其相对密度为62％；
将ITO陶瓷生坯体干燥，之后放入脱脂烧结一体炉中，脱脂温度为750℃，时间为24小时，脱脂结束后直接以3℃/min升温速率升至最高烧结温度1600℃，然后在该烧结温度下保温24小时，烧结气氛为常压高纯氧气。
比较例1得到的ITO陶瓷靶材的相对密度为97.4％，电阻率为0.19mΩ·cm，其微观组织形貌如图4所示，平均晶粒尺寸为11.5μm，陶瓷内部没能完全致密化，仍有少许孔洞，原因是混合粉体处理不到位，粉体的烧结活性不够。
比较例2
本比较例2制备晶粒尺寸可控ITO陶瓷靶材的方法包括：
分别称重450g In2O3粉体和50g SnO2粉体；9g聚丙烯酸、2.5g阿拉伯树胶、9g丙烯酰胺和125g去离子水组成预混液；
将两种氧化物粉体和预混液加入滚筒球磨罐中混合，然后将浆料转移至砂磨机中高能球磨，将球磨罐的真空度抽至9Pa，球磨1小时，得到粉体固体质量含量为80％的ITO浆料，激光粒度仪测得混合粉体平均粒径分布D50为400nm；
将浆料注入石膏模具中，在压力为0.2MPa条件下成形，得到ITO陶瓷生坯体，其相对密度为62％；
将ITO陶瓷生坯体干燥，之后放入脱脂烧结一体炉中，脱脂温度为750℃，时间为24小时，脱脂结束后直接以3℃/min升温速率升最高烧结温度1600℃，然后在该烧结温度下保温24小时，烧结气氛为常压高纯氧气。
比较例2得到的ITO陶瓷靶材的相对密度为97.8％，电阻率为0.18mΩ·cm，其微观组织形貌如图5所示，平均晶粒尺寸为9.5μm，陶瓷内部没能完全致密化，仍有少许孔洞，原因是混合粉体处理不到位，粉体的烧结活性不够。
比较例3
本比较例3制备晶粒尺寸可控ITO陶瓷靶材的方法包括：
分别称重450g In2O3粉体和50g SnO2粉体；9g聚丙烯酸、2.5g阿拉伯树胶、9g丙烯酰胺和125g去离子水组成预混液；
将两种氧化物粉体和预混液加入滚筒球磨罐中混合，球磨1小时，然后将浆料转移至砂磨机中高能球磨，将球磨罐抽真空9Pa，得到粉体固体质量含量为80％的ITO浆料，激光粒度仪测得混合粉体平均粒径分布D50为200nm；
将浆料注入石膏模具中，在压力为0.05MPa条件下成形，得到ITO陶瓷生坯体，其相对密度为57％；
将ITO陶瓷生坯体干燥，之后放入脱脂烧结一体炉中，脱脂温度为750℃，时间为24小时，脱脂结束后直接以3℃/min升温速率升至最高烧结温度1600℃，在该烧结温度下保温24小时，烧结气氛为常压高纯氧气。
比较例3得到的ITO陶瓷靶材的相对密度为98.2％，电阻率为0.17mΩ·cm，其微观组织形貌如图6所示，平均晶粒尺寸为11.5μm，陶瓷内部没能完全致密化，仍有少许孔洞，原因是ITO陶瓷生坯相对密度不够，达不到该烧结工艺的要求。
相对于实施例1～3，对比例1～3得到的ITO陶瓷靶材相对密度小，电阻率高，烧结体没能完全致密化。
本申请实施例公开的晶粒尺寸可控ITO陶瓷靶材的制备方法，从粉体一次粒径分布、混合粉体球磨分散粒径分布、成形工艺及烧结工艺等协同优化组合，ITO陶瓷靶材晶体结构等方面进行了创新研究，制备得到了晶粒尺寸可控的ITO陶瓷靶材，拥有优异的电学和力学等性能，利于制备高质量ITO薄膜。工艺操作简便，生坯烧结性好，便于制备各种尺寸的ITO陶瓷靶材，且ITO陶瓷靶材密度高、电阻率低、晶粒细小且粒度分布均匀，其相对密度可达99.7％，电阻率低至0.13mΩ·cm，晶粒尺寸可控，其数值可以低至3～5μm，降低的烧结温度可以相应的降低生产成本，延长设备使用寿命，适用于工业化生产。
本申请公开的技术方案和实施例中公开的技术细节，仅是示例性说明本申请的构思，并不构成对本申请技术方案的限定，凡是对本申请公开的技术细节所做的没有创造性的改变，都与本申请具有相同的发明构思，都在本申请权利要求的保护范围之内。

Claims (5)

1.一种晶粒尺寸可控ITO陶瓷靶材的制备方法，其特征在于，该制备方法包括以下步骤：
将质量份数为90~97的In2O3粉体和质量份数为10~3的SnO2粉体，与去离子水、稀释剂、粘结剂和高分子材料用砂磨机球磨混合，得到固含量在70~80%之间、粘度在120~300mpa.s之间的ITO陶瓷浆料，且所述ITO陶瓷浆料中混合粉体的平均粒径D50控制在200~300nm；其中，所述In2O3粉体的一次颗粒粒径分布范围为80~200nm，所述SnO2粉体的一次颗粒粒径分布范围为80~200nm，所述稀释剂为聚丙烯酸类或聚羧酸类稀释剂，所述粘结剂为阿拉伯树胶、聚乙烯醇或丙烯酸树脂，所述高分子材料为聚丙烯酰胺；
ITO陶瓷浆料经压力注浆成形，得到相对密度为58~62%的ITO陶瓷生坯体；
ITO陶瓷生坯体经一体化脱脂烧结处理，得到ITO陶瓷靶材；其中，所述一体化脱脂烧结处理具体包括：
将ITO陶瓷生坯体放入脱脂烧结一体化炉；
将脱脂烧结一体化炉以升温速率1～3℃/min加热至脱脂温度700~800℃，将ITO陶瓷靶材在常压氧气氛中进行脱脂处理，脱脂时间设定为12～36小时；
将脱脂烧结一体化炉从脱脂温度以升温速率2～5 ℃/min升温到第一烧结温度1600～1650℃；
升温到第一烧结温度后，在第一烧结温度保温0～60min，随即开始将脱脂烧结一体化炉从第一烧结温度以降温速率8～16 ℃/min降低到第二烧结温度1500～1540℃，将ITO靶材在第二烧结温度、常压氧气氛中进行烧结处理，保温12～36小时，最终得到ITO陶瓷靶材。
2.根据权利要求1所述的制备方法，其特征在于，所述In2O3粉体和所述SnO2粉体的质量份数为90和10。
3.根据权利要求1所述的制备方法，其特征在于，所述In2O3粉体和所述SnO2粉体的质量份数为95和5。
4.根据权利要求1所述的制备方法，其特征在于，所述In2O3粉体和所述SnO2粉体的质量份数为93和7。
5.根据权利要求1所述的制备方法，其特征在于，所述球磨混合在真空负压条件下进行，负压压力不大于9Pa。
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