CN106904953B - 高密度封装用高热膨胀系数陶瓷材料及其制备方法 - Google Patents

高密度封装用高热膨胀系数陶瓷材料及其制备方法 Download PDF

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CN106904953B
CN106904953B CN201710181323.9A CN201710181323A CN106904953B CN 106904953 B CN106904953 B CN 106904953B CN 201710181323 A CN201710181323 A CN 201710181323A CN 106904953 B CN106904953 B CN 106904953B
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李波
李威
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University of Electronic Science and Technology of China
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Abstract

本发明属于电子陶瓷封装材料技术领域,提供一种高密度封装用高热膨胀系数陶瓷材料及其制备方法,用以克服现有芯片封装材料热失配的问题;本发明陶瓷材料的组分包括:SiO2:55~70wt%,BaO:20~30wt%,B2O3:5~10wt%,Al2O3:2~5wt%,Y2O3:0.1~1wt%,及CrO2与ZrO2混合物:1~3wt%。本发明陶瓷材料热膨胀系数为12~15ppm/℃,与PCB板热膨胀系数(12~18ppm/℃)相匹配;抗弯强度高达170~240MPa,杨氏模量为50~70GPa,力学性能优异,能够完全克服热失配等问题;同时,材料介电常数小、损耗低,性能稳定,能够满足高密度封装的需求;另外其制备工艺简单成熟、节能高效,符合工业化生产的要求,便于批量生产以及推广应用。

Description

高密度封装用高热膨胀系数陶瓷材料及其制备方法
技术领域
本发明属于电子陶瓷封装材料技术领域,尤其涉及高密度封装材料,具体提供一种高密度封装用高热膨胀系数陶瓷材料及其制备方法。
背景技术
由于电子信息产业推动着集成电路系统不断朝着高密度化、超大规模化和多功能化的方向发展,这使得电子封装技术成为芯片制造技术和系统集成技术中独立而又不可或缺的技术体系。电子封装材料在封装技术中又起到至关重要的作业,其主要对芯片提供机械支持、电气连接、散热防潮、应力缓和等物理保护作用。而这些功能的实现,都依赖于电子封装材料的综合性能。因为陶瓷封装材料由于其在电、热、机械特性等方面性能稳定,而且其性能可以通过改变其化学成分和调整工艺来实现,所以在目前的高端芯片制造中大多采用最先进的多层陶瓷球栅阵列封装技术。
传统的Al2O3、AIN、BeO和SiC等陶瓷封装材料,由于工艺温度高,成型能力弱等问题,无法满足高密度封装技术的发展需求,因此出现了低温共烧陶瓷(LTCC)材料。目前,低温共烧陶瓷(LTCC)材料的研发已成为电子封装领域的研究热点,而LTCC技术已被广泛应用于微波、射频等器件的单芯片或组件的封装,在无线通信领域起着极为重要的作用。目前,高密度封装广泛采用多层陶瓷球栅阵列封装结构,而将LTCC模块用植球技术封装在PCB板上存在热失配等问题。对于陶瓷封装材料而言,因为高密度封装的需求,这类材料通常需要介电常数低,损耗小,机械性能优异以及高热膨胀系数以实现基板和金属涂层的热匹配。但是,目前的陶瓷封装材料仍然普遍存在机械强度低,热膨胀偏小等缺点,所以开发具有高热膨胀系数高强度的LTCC材料迫在眉睫。
如公开号为:CN 1002898027B、发明名称为“电子元器件封装材料用陶瓷粉及其生产方法”的专利中公开了一种陶瓷粉的制备方法,该陶瓷包括45wt%的含BaO、B2O3、SiO2、Al2O3的复合氧化物及55wt%的石英粉,其抗弯强度为150~175MPa。而在申请号为:201610365136.1、发明名称为“一种高热膨胀系数陶瓷材料及其制备方法”的专利中公开了一种钙硼硅玻璃为主的电子封装陶瓷材料,其配方采用35~85wt%组成为CaO、B2O3、SiO2、Al2O3的钙硼硅复合氧化物及15~65wt%石英砂,所得陶瓷材料以硅灰石、石英成为主晶相,热膨胀系数(CTE)为8.5~12.5ppm/℃,与PCB板(热膨胀系数12~18ppm/℃)相比依然较低,仍然不能有效的解决热失陪问题;此外,上述两份专利文件中材料的制备过程复杂,分为复合氧化物和陶瓷粉的合成两步完成。
对于大规模集成电路高密度封装材料的研究,欧美等发达国家走在世界前列。美国康宁公司的名称为“高膨胀环硅酸盐玻璃-陶瓷”(CN 101421199B)的专利公开了一种玻璃陶瓷的制备方法,其包含(以重量百分比计)30~55%SiO2、5~40%CaO、0~50%BaO、0~40%SrO和0.1~10%Al2O3。其熔制温度高达1450-1650℃,不但耗能巨大,且对耐火材料要求高,成分中易挥发物质在熔融过程中的损耗难以控制,不适合工业化生产。该玻璃陶瓷热膨胀系数为8.5~11.5ppm/℃,相对PCB板而言依然较低,也未注明材料的介电性能和力学性能。其作用主要是作为密封剂和金属、金属合金及陶瓷的高性能涂层,故其并不适用于高密度封装。
基于此,目前需要研究出一种应用于高密度封装的高热膨胀系数低温共烧陶瓷材料,在有效解决热失配问题的同时,具备优异的机械性能、介电性能等,以满足高密度封装技术的需求。
发明内容
本发明的目的在于针对上述背景技术中的弊端,提供一种高密度封装用高热膨胀系数低温共烧陶瓷材料及其制备方法;该高热膨胀系数低温共烧陶瓷材料介电常数小、损耗低,热膨胀系数与PCB板相匹配,抗弯强度高,材料性能稳定。此外,其制备工艺简单成熟、节能高效,符合工业化生产的要求,便于批量生产以及推广应用。
为实现上述目的,本发明采用的技术方案为:
高密度封装用高热膨胀系数陶瓷材料,其特征在于,以质量百分比计,所述陶瓷材料的组分包括:SiO2:55~70wt%,BaO:20~30wt%,B2O3:5~10wt%,Al2O3:2~5wt%,Y2O3:0.1~1wt%,及CrO2与ZrO2混合物:1~3wt%。
进一步的,所述CrO2与ZrO2混合物为两者任意比例的混合物。
上述高密度封装用高热膨胀系数陶瓷材料的制备方法,包括以下步骤:
步骤1:以氢氧化钡、硼酸、二氧化硅、氢氧化铝、氢氧化锆、氧化钇、氧化铬为原料,按配方进行配料;
步骤2:将步骤1中各原料混合均匀,经球磨、烘干、过筛后得到干燥粉体;
步骤3:将步骤2所得干燥粉体置于650~750℃下预烧1~3小时得到预烧料;
步骤4:将步骤3所得预烧料进行造粒,干压成型;
步骤5:将步骤4中干压成型样品经排胶处理后,于800~950℃下烧结1~3小时,自然冷却后即得到高热膨胀系数陶瓷材料。
上述制备过程中采用低温共烧,工艺简洁成熟,节能环保,所制备材料性能稳定。本发明制备的高膨胀系数低温共烧陶瓷材料介电性能优良,介电常数小(5~6),损耗低(tanδ<4.0×10-3),热膨胀系数为12~15ppm/℃,抗弯强度高达170~240MPa,杨氏模量为50~70GPa,为数字、模拟、微波、射频等器件的单芯片或组件的高密度封装提供了更好的解决方案。
综上,本发明的有益效果在于:
1、本发明的高热膨胀系数低温共烧陶瓷材料热膨胀系数为12~15ppm/℃,与PCB板热膨胀系数(12~18ppm/℃)相匹配;抗弯强度高达170~240MPa,杨氏模量为50~70GPa,力学性能优异,能够完全克服热失配等问题;同时,材料介电常数小(5~6)、损耗低(tanδ<4.0×10-3),性能稳定,能够满足高密度封装的需求;
2、本发明提供制备工艺简单成熟、节能高效,符合工业化生产的要求,便于批量生产以及推广应用;
3、本发明除上述用于高密度封装领域外,也可以应用于材料封接领域,如固体氧化物燃料电池,真空电子管的制造等。
附图说明
图1为实施例3所制备的高热膨胀系数低温共烧陶瓷材料的XRD衍射分析图。
图2为实施例3所制备的高热膨胀系数低温共烧陶瓷材料的断面扫描电镜SEM图。
具体实施方式
以下结合具体实施例对本发明进行进一步的描述。
表1为本发明实施例1~5具有高膨胀系数低温共烧陶瓷材料各组分实际配比和制备工艺,表2为本发明实施例1~5的各项性能;其中实施例3制备得高热膨胀系数低温共烧陶瓷材料的XRD衍射分析图和断面扫描电镜SEM图如图1、图2所示。
高密度封装用高热膨胀系数陶瓷材料具体制备过程如下:
步骤1:以氢氧化钡、硼酸、二氧化硅、氢氧化铝、氢氧化锆、氧化钇、氧化铬为原料,按表1中具体实施例的所述配方进行配料;
步骤2:将步骤1中各原料混合均匀,经球磨、烘干、过筛后得到干燥粉体;
步骤3:由步骤2所得干燥粉体置于650~750℃下预烧1~3小时得到预烧料;
步骤4:由步骤3所得预烧料进行造粒,干压成型;
步骤5:将步骤4中干压成型样品经排胶处理后,于800~950℃下烧结1~3小时,自然冷却后即得到高热膨胀系数低温共烧陶瓷材料,测试结果如表2。
表1
Figure BDA0001253642950000041
表2
Figure BDA0001253642950000042
以上所述,仅是本发明一种高膨胀系数低温共烧陶瓷材料及其制备方法的有限实施例而已,并非对本发明的技术范围作任何限制,凡是依据本发明的技术实质对以上实施例所作的任何修改或等同变化,均属于本发明技术方案的范围内。

Claims (3)

1.高密度封装用高热膨胀系数陶瓷材料,其特征在于,以质量百分比计,所述陶瓷材料由以下组分组成:SiO2:55~70 wt%,BaO:20~30 wt%,B2O3:5~10 wt%,Al2O3:2~5 wt%,Y2O3:0.1~1 wt%,及CrO2与ZrO2混合物:1~3 wt%;所述陶瓷材料的抗弯强度为189~240MPa,杨氏模量为58~69GPa。
2.按权利要求1所述高密度封装用高热膨胀系数陶瓷材料,其特征在于,所述CrO2与ZrO2混合物为两者任意比例的混合物。
3.按权利要求1所述高密度封装用高热膨胀系数陶瓷材料的制备方法,包括以下步骤:
步骤1:以氢氧化钡、硼酸、二氧化硅、氢氧化铝、氢氧化锆、氧化钇、二氧化铬为原料,按配方进行配料;
步骤2:将步骤1中各原料混合均匀,经球磨、烘干、过筛后得到干燥粉体;
步骤3:将步骤2所得干燥粉体置于650~750℃下预烧1~3小时得到预烧料;
步骤4:将步骤3所得预烧料进行造粒,干压成型;
步骤5:将步骤4中干压成型样品经排胶处理后,于800~950℃下烧结1~3小时,自然冷却后即得到高热膨胀系数陶瓷材料。
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