CN112745126B - 一种Si3N4晶须增韧的高导热AlN陶瓷基板和制备方法 - Google Patents

一种Si3N4晶须增韧的高导热AlN陶瓷基板和制备方法 Download PDF

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CN112745126B
CN112745126B CN202011520575.8A CN202011520575A CN112745126B CN 112745126 B CN112745126 B CN 112745126B CN 202011520575 A CN202011520575 A CN 202011520575A CN 112745126 B CN112745126 B CN 112745126B
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aluminum nitride
polyethylene glycol
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slurry
ball milling
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吴超
李华冠
张旭
张博森
权静茹
霍可心
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Nanjing Institute of Technology
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Abstract

本发明提供了一种Si3N4晶须增韧的高导热AlN陶瓷基板和制备方法。制备方法，包括以下步骤：第一步：将氮化铝粉体、氧化钇、聚氮硅烷纤维、聚乙二醇缩丁醛、聚乙二醇和乙醇进行混合，在水浴下得到混合料浆；第二步：将混合料浆放入聚四氟乙烯罐中球磨，第三步：将球磨后料浆进行过筛除泡后得到流延浆料；第四步：流延浆料经过流延工艺得到复相陶瓷胶片；第五步：将第四步得到的复相陶瓷胶片进入脱脂炉内进行排胶，得到复相陶瓷的素片；第六步：将第五步中得到的复相陶瓷的素片在氮气气氛下烧结，得到产品。本发明在尽可能不影响氮化铝热导率的条件下，借助晶须桥联、拔出和裂纹偏转作用，提高氮化铝陶瓷的断裂韧性，提高氮化铝基片的可靠性。

Description

一种Si3N4晶须增韧的高导热AlN陶瓷基板和制备方法
技术领域
本发明属于晶须增韧陶瓷基片材料领域。涉及一种Si3N4晶须增韧的高导热AlN陶瓷基板和制备方法。
背景技术
随着大规模集成电路的发展，人们对于封装用基片的要求也越来越严格。其中，高电阻率、高热导率和低介电常数是集成电路对封装用基片的最基本要求。封装用基片还应与硅片具有良好的热匹配、易成型、高表面平整度、易金属化、易加工、低成本等特点和一定的力学性能。
氮化铝（AlN）作为一种综合性能优良新型的先进陶瓷材料，具有优良的热传导性，可靠的电绝缘性，低的介电常数和介电损耗，无毒以及与硅相匹配的热膨胀系数等一系列优良特性，被认为是新一代高集程度半导体基片和电子器件封装的理想材料，受到了国内外研究者的广泛重视。在理论上，AlN的热导率为320W/(m·K)，工业上实际制备的多晶氮化铝的热导率也可达100~250 W/(m)，该数值是传统基片材料氧化铝热导率的5倍～10倍；但强共价键的存在大大降低了氮化铝陶瓷的断裂韧性，使其在高功率LED照明和大功率集成电路的冷热交替服役环境中的可靠性大幅下降。
氮化硅与氮化铝陶瓷有良好的物理化学性能相容性，单晶理论热导率达400W/(m·K)，受限于制备工艺，其商用制品热导率仅为80~100 W/(m·K)；但其力学性能优异，弯曲强度可达600~800MPa，断裂任性为7~9MPa·m1/2。随着氮化硅产业的发展，其晶须产品逐渐成为一种潜在的陶瓷增强体，相比碳纤维具有更加优异的绝缘性能，可以用于电子封装陶瓷的增韧。因此，本发明的目的在于尽可能不影响氮化铝陶瓷热导率的基础上，引入氮化硅晶须改善基体陶瓷的韧性，改善氮化铝陶瓷的服役可靠性。
发明内容
1、所要解决的技术问题：
工业上实际制备的多晶氮化铝热导率，但是强共价键的存在降低了氮化铝陶瓷的断裂韧性。由于目前高功率电子封装基板用氮化铝断裂韧性较差，无法实现高低温转换的高可靠性需求
2、技术方案：
针对目前高功率电子封装基板用氮化铝断裂韧性较差，无法实现高低温转换的高可靠性需求，本发明提供了一种Si3N4晶须增韧的高导热AlN陶瓷基板的制备方法，包括以下步骤：第一步：将氮化铝粉体、氧化钇、聚氮硅烷纤维、聚乙二醇缩丁醛、聚乙二醇和乙醇进行混合，在水浴下得到混合料浆；第二步：将混合料浆放入聚四氟乙烯罐中球磨，第三步：将球磨后料浆进行过筛除泡后得到流延浆料；第四步：流延浆料经过流延工艺得到复相陶瓷胶片；第五步：将第四步得到的复相陶瓷胶片进入脱脂炉内进行排胶，得到复相陶瓷的素片；第六步：将第五步中得到的复相陶瓷的素片在氮气气氛下烧结，得到产品。
所述氮化铝粉体的平均粒径为0.9-1.1μm；所述氮化钇的平均粒径为0.4-0.6μm；所述聚氮硅烷纤维直径为0.9-1.1μm，长度平均为45-55μm；所述聚乙二醇缩丁醛的聚合度为2000~2100；所述聚乙二醇的分子量为3600-4400。
所述铝粉体、氧化钇、聚氮硅烷纤维、聚乙二醇缩丁醛、聚乙二醇和乙醇的质量比为：0.9-1.1:0.02-0.04:0.09-0.11:2.7-3.3:1.8-2.2:18-22。
在第一步中，水浴的温度为65-75℃，通过磁力搅拌得到混合料浆。
所述磁力搅拌为0.9-1.1小时。
在第二步中，所述球磨的时间为7-9小时，所述球磨的介质为氮化铝球。
在第五步中，所述排胶的温度为450-500℃，所述排胶时间为7-9小时，升温速率为27-33℃每小时。
在第六步中：所述烧结的条件为：1780℃~1830℃条件下烧结4-8h。
在烧结过程中，升温速度为升温速度为0-800℃升温速率为9-11℃/分钟，800℃时保温2-4h，800℃以上升温速率为4-6℃/分钟。
一种使用所述的方法制备的Si3N4晶须增韧的高导热AlN陶瓷基板，由氮化铝基体和氮化硅晶须构成，其中，氮化硅晶须的质量比2wt.%。
3、有益效果：
本发明提供的Si3N4晶须增韧的高导热AlN陶瓷基板，选取聚氮硅烷作为氮化硅晶须的前驱体，不仅仅可以大幅降低原料的成本；此外，由于聚氮硅烷韧性较氮化硅晶须较好，可以保证在球磨过程中不发生断裂，在高温裂解后最大程度上保证晶须的结构完整性和长径比。
本发明利用前驱体裂解法引入的氮化硅晶须具有较高的长径比、弹性模量、导热系数和较低的热膨胀系数，与氮化铝基体的物理化学性能匹配，借助晶须桥联、拔出和裂纹偏转作用，可以显著提高氮化铝陶瓷的断裂韧性，提高氮化铝基片在不断冷热交替环境下的热稳定性和可靠性。本发明通过对排胶工艺和烧结工艺的控制，对烧结过程中氮化硅晶须生成及烧结致密化过程具有显著影响，进而影响产品的最终性能。本发明所采用的烧结工艺，所制备的产品结构致密，力学性能优异。
附图说明
图1为本发明所述氮化硅晶须增韧氮化铝基板的制备工艺流程。
图2为实施例1中高温裂解所得的氮化硅晶须SEM图。
图3为实施例1中氮化硅晶须增韧氮化铝基板的断面SEM图。
具体实施方式
下面结合附图和实施例来对本发明进行详细说明。
如图1所示，一种Si3N4晶须增韧的高导热AlN陶瓷基板的制备方法，包括以下步骤：第一步：将氮化铝粉体、氧化钇、聚氮硅烷纤维、聚乙二醇缩丁醛、聚乙二醇和乙醇进行混合，在水浴下得到混合料浆；第二步：将混合料浆放入聚四氟乙烯罐中球磨，第三步：将球磨后料浆进行过筛除泡后得到流延浆料；第四步：流延浆料经过流延工艺得到复相陶瓷胶片；第五步：将第四步得到的复相陶瓷胶片进入脱脂炉内进行排胶，得到复相陶瓷的素片；第六步：将第五步中得到的复相陶瓷的素片在氮气气氛下烧结，得到产品。
本发明提供的方法借助氮化硅晶须具有较高的长径比、弹性模量、导热系数和较低的热膨胀系数，与氮化铝基体物理化学性能良好的匹配，在尽可能不影响氮化铝热导率的条件下，借助晶须桥联、拔出和裂纹偏转作用，提高氮化铝陶瓷的断裂韧性，提高氮化铝基片的可靠性。
对比例1
将氮化铝粉体（平均粒径为1μm）、氧化钇（平均粒径为0.5μm）、聚乙二醇缩丁醛（聚合度为2000~2100）、聚乙二醇（分子量为4000）和乙醇按照1:0.03: 3:2:20质量比进行混合（氧化钇作为烧结助剂），在水浴70℃下进行磁力搅拌1h得到混合料浆；之后将混合料浆放入聚四氟乙烯罐中球磨8h，球磨介质为氮化铝球，球磨后料浆进行过筛除泡后得到流延浆料；流延浆料经过流延工艺后得到复相陶瓷胶片，之后进入脱脂炉内进行排胶，排胶温度为480℃，排胶时间为8h，升温速率为30℃/小时得复相陶瓷的素片；复相陶瓷素片于氮气气氛，1800℃条件下烧结4h，升温速度为0-800℃升温速率为10℃/分钟，800℃时保温3h，800℃以上升温速率为5℃/分钟，得到纳米氧化铝增强氮氧化铝陶瓷，其相对密度为98.8%；抗弯强度为281.2MPa；断裂韧性为：2.32MPa·m1/2；热导率为169.2W/(m·K)。未引入氮化硅晶须的氮化铝陶瓷基板抗弯强度和断裂韧性较差，尤其断裂韧性相较实施例1下降了70%。
实施例1
将氮化铝粉体、氧化钇、聚氮硅烷纤维、聚乙二醇缩丁醛、聚乙二醇和乙醇按照1:0.03:0.1:3:2:20质量比进行混合，所述氮化铝粉体的平均粒径为1μm；所述氮化钇的平均粒径为0.5μm；所述聚氮硅烷纤维直径为1μm，长度平均为50μm；所述聚乙二醇缩丁醛的聚合度为2000，所述聚乙二醇的分子量为4000其中氧化钇作为烧结助剂，在水浴70℃下进行磁力搅拌1h得到混合料浆；之后将混合料浆放入聚四氟乙烯罐中球磨8h，球磨介质为氮化铝球，球磨后料浆进行过筛除泡后得到流延浆料；流延浆料经过流延工艺后得到复相陶瓷胶片，之后进入脱脂炉内进行排胶，排胶温度为480℃，排胶时间为8h，升温速率为30℃/小时得复相陶瓷的素片；复相陶瓷素片于氮气气氛，1830℃条件下烧结8h，升温速度为0-800℃升温速率为10℃/分钟，800℃时保温3h，800℃以上升温速率为5℃/分钟，得到纳米氧化铝增强氮氧化铝陶瓷，其相对密度为99.6%；抗弯强度为387.5MPa；断裂韧性为：7.64MPa·m1 /2；热导率为192.8W/(m·K)。
图2为裂解后的氮化硅晶须形貌，图3为氮化硅晶须增韧氮化铝基板的断面形貌，氮化硅晶须形貌完整，与基体结合优异。
实施例2
将氮化铝粉体、氧化钇、聚氮硅烷纤维、聚乙二醇缩丁醛、聚乙二醇和乙醇按照1:0.03:0.1:3:2:20质量比进行混合，所述氮化铝粉体的平均粒径为1.1μm；所述氮化钇的平均粒径为0.4μm；所述聚氮硅烷纤维直径为1.1μm，长度平均为45μm；所述聚乙二醇缩丁醛的聚合度为2100；所述聚乙二醇的分子量为3600，其中氧化钇作为烧结助剂，在水浴70℃下进行磁力搅拌1h得到混合料浆；之后将混合料浆放入聚四氟乙烯罐中球磨8h，球磨介质为氮化铝球，球磨后料浆进行过筛除泡后得到流延浆料；流延浆料经过流延工艺后得到复相陶瓷胶片，之后进入脱脂炉内进行排胶，排胶温度为480℃，排胶时间为8h，升温速率为30℃/小时得复相陶瓷的素片；复相陶瓷素片于氮气气氛，1780℃条件下烧结4h，升温速度为0-800℃升温速率为10℃/分钟，800℃时保温3h，800℃以上升温速率为5℃/分钟，得到纳米氧化铝增强氮氧化铝陶瓷，其相对密度为98.7%；抗弯强度为295.6MPa；断裂韧性为：5.82MPa·m1/2；热导率为160.2W/(m·K)。
实施例3
将氮化铝粉体、氧化钇、聚氮硅烷纤维、聚乙二醇缩丁醛、聚乙二醇和乙醇按照0.9:0.04:0.09:3.3:1.8:22质量比进行混合，所述氮化铝粉体的平均粒径为0.9μm；所述氮化钇的平均粒径为0.6μm；所述聚氮硅烷纤维直径为1.1μm，长度平均为55μm；所述聚乙二醇缩丁醛的聚合度为2000；所述聚乙二醇的分子量为4400，其中氧化钇作为烧结助剂，在水浴65℃下进行磁力搅拌1.1h得到混合料浆；之后将混合料浆放入聚四氟乙烯罐中球磨7h，球磨介质为氮化铝球，球磨后料浆进行过筛除泡后得到流延浆料；流延浆料经过流延工艺后得到复相陶瓷胶片，之后进入脱脂炉内进行排胶，排胶温度为500℃，排胶时间为9h，升温速率为27℃/小时得复相陶瓷的素片；复相陶瓷素片于氮气气氛，1820℃条件下烧结8h，升温速度为0-800℃升温速率为11℃/分钟，800℃时保温4h，800℃以上升温速率为4℃/分钟，得到纳米氧化铝增强氮氧化铝陶瓷，其相对密度为98.5%；抗弯强度为305.6MPa；断裂韧性为：6.12MPa·m1/2；热导率为168.2W/(m·K)。
实施例4
将氮化铝粉体、氧化钇、聚氮硅烷纤维、聚乙二醇缩丁醛、聚乙二醇和乙醇按照1.1:0.02:0.11:2.7:2.2:18质量比进行混合，所述氮化铝粉体的平均粒径为1.1μm；所述氮化钇的平均粒径为0.5μm；所述聚氮硅烷纤维直径为0.9μm，长度平均为50μm；所述聚乙二醇缩丁醛的聚合度为2050；所述聚乙二醇的分子量为3800，其中氧化钇作为烧结助剂，在水浴75℃下进行磁力搅拌0.9h得到混合料浆；之后将混合料浆放入聚四氟乙烯罐中球磨9h，球磨介质为氮化铝球，球磨后料浆进行过筛除泡后得到流延浆料；流延浆料经过流延工艺后得到复相陶瓷胶片，之后进入脱脂炉内进行排胶，排胶温度为450℃，排胶时间为7h，升温速率为33℃/小时得复相陶瓷的素片；复相陶瓷素片于氮气气氛，1800℃条件下烧结6h，升温速度为0-800℃升温速率为11℃/分钟，800℃时保温4h，800℃以上升温速率为4℃/分钟，得到纳米氧化铝增强氮氧化铝陶瓷，其相对密度为98.6%；抗弯强度为300.6MPa；断裂韧性为：5.88MPa·m1/2；热导率为169.2W/(m·K)。
所述实施例1-4中所得的氮化硅晶须增韧氮化铝基板的相对密度均大于98%，热导率均大于160.2W/(m·K)，达到了商用高导热基板的要求，力学性能也相较于纯相氮化铝有了明显改善，且微观结构良好。

Claims (2)

1.一种Si3N4晶须增韧的高导热AlN陶瓷基板的制备方法，包括以下步骤：第一步：将氮化铝粉体、氧化钇、聚氮硅烷纤维、聚乙二醇缩丁醛、聚乙二醇和乙醇进行混合，在水浴下得到混合料浆；第二步：将混合料浆放入聚四氟乙烯罐中球磨，第三步：将球磨后料浆进行过筛除泡后得到流延浆料；第四步：流延浆料经过流延工艺得到复相陶瓷胶片；第五步：将第四步得到的复相陶瓷胶片进入脱脂炉内进行排胶，得到复相陶瓷的素片；第六步：将第五步中得到的复相陶瓷的素片在氮气气氛下烧结，得到产品；
所述氮化铝粉体的平均粒径为0.9-1.1μm；所述氧化钇的平均粒径为0.4-0.6μm；所述聚氮硅烷纤维直径为0.9-1.1μm，长度平均为45-55μm；所述聚乙二醇缩丁醛的聚合度为2000~2100；所述聚乙二醇的分子量为3600-4400；
所述铝粉体、氧化钇、聚氮硅烷纤维、聚乙二醇缩丁醛、聚乙二醇和乙醇的质量比为：0.9-1.1 : 0.02-0.04 : 0.09-0.11 : 2.7-3.3 : 1.8-2.2 : 18-22；
在所述第一步中，所述水浴的温度为65-75℃，通过磁力搅拌得到混合料浆，
所述磁力搅拌为0.9-1.1小时；
在第二步中，所述球磨的时间为7-9小时，所述球磨的介质为氮化铝球；
在第五步中，所述排胶的温度为450-500℃，所述排胶时间为7-9小时，升温速率为27-33℃每小时；
在第六步中：所述烧结的条件为：1780℃-1830℃条件下烧结4-8h；
在烧结过程中，升温速度为：0-800℃升温速率为9-11℃/分钟，800℃时保温2-4h，800℃以上升温速率为4-6℃/分钟。
2.一种使用如权利要求1所述的方法制备的Si3N4晶须增韧的高导热AlN陶瓷基板，其特征在于：由氮化铝基体和氮化硅晶须构成，其中，氮化硅晶须的质量比2wt.%。
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