CN112341178B - 一种宽频低膨胀系数低温共烧玻璃复合陶瓷及其制备方法 - Google Patents

一种宽频低膨胀系数低温共烧玻璃复合陶瓷及其制备方法 Download PDF

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CN112341178B
CN112341178B CN202011227059.6A CN202011227059A CN112341178B CN 112341178 B CN112341178 B CN 112341178B CN 202011227059 A CN202011227059 A CN 202011227059A CN 112341178 B CN112341178 B CN 112341178B
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周洪庆
陆阳
罗现福
单怡婷
杨诚宇
曹桃桃
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Nanjing Tech University
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Abstract

本发明提供了一种宽频低膨胀系数低温共烧玻璃复合陶瓷及其制备方法，其特征是由玻璃复合陶瓷多层生料带及其印刷相应的贵金属浆料厚膜所组成；其中生料带中原料组分由低膨胀系数的玻璃料、低膨胀系数的陶瓷料、有机流延体系三部分组成。将宽频低损耗低膨胀系数多元玻璃料，从高温熔化的流动态玻璃液，倒入水中淬冷，得到玻璃渣，通过球磨得到玻璃粉，按照配比将低膨胀系数的玻璃粉、陶瓷粉，混合为复合粉料，与有机体系配成浆料，流延成生瓷料带，印刷金属、介质浆料，在650‑920℃低温共烧获得致密的宽频低损耗玻璃陶瓷材料。该玻璃陶瓷具有相对介电常数4.0到15.0连续可调、宽频低损耗、频率温度稳定性好等特点。是一种具有广泛应用前景的新型封装材料。

Description

一种宽频低膨胀系数低温共烧玻璃复合陶瓷及其制备方法
技术领域
本发明涉及一种宽频低膨胀系数低温共烧玻璃复合陶瓷及其制备方法，适用于宽频大规模混合集成电路封装，具有宽频热膨胀系数低的玻璃、陶瓷配方，以及多元玻璃料、多类陶瓷料与多种有机体系配比的成分范围，形成低温共烧多层含厚膜印刷电路的玻璃陶瓷制备方法，属于有机/无机/金属复合材料领域。
背景技术
随着高端信息系统大尺寸混合集成电路(HIC)、微波多芯片组件(MCM)等宽频微波毫米波技术的快速发展。对制造高频宽频互联电路的封装材料与多层印刷厚膜基片要求越来越迫切。美国休斯公司1982年提出的低温共烧陶瓷(Low Temperature Co-firedCeramics，LTCC)新技术，使得二维封装快速向高可靠的立体三微系统封装推进。在高端信息智能科技领域，有着广泛而迫切的应用需求。
LTCC以功能复合新材料为基础，以精密高效的流延制备生瓷带为特征，这种材料具有布线间距宽(布线宽度和间距可小至0.003inch)、设计灵活、埋置多种无源元件、可靠性高、低阻抗金属化及高频特性优异等许多优点。因此美国、日本等发达国家对LTCC材料体系的研究高度关注，且对我国封锁。目前国内对高性能特别是含模块级以上的LTCC材料的研究处于起步阶段，拥有自主知识产权的、低膨胀系数玻璃、陶瓷及其相关复合材料体系尚未见报导，商品化高性能宽频低损耗模块封装用LTCC材料国内尚为空白。
发明内容
本发明的目的在于为了改进现有技术的不足而提供一种宽频低膨胀系数低温共烧玻璃复合陶瓷，本发明的另一目的是提供上述频低膨胀系数低温共烧玻璃复合陶瓷的制备方法。本发明提供了一种适用于1MHz-100GHz超宽频率范围，具有低损耗的模块或系统级微电路封装材料，具有低软化点多元玻璃料、陶瓷料配方，玻璃复合陶瓷以及有机体系配比的成分范围，生瓷带及其低温共烧多层微电路基片的制备方法。
本发明的技术方案为：一种宽频低膨胀系数低温共烧玻璃复合陶瓷，其特征是由玻璃复合陶瓷多层生料带及其印刷相应的贵金属浆料厚膜所组成；其中生料带中原料组分由低膨胀系数的玻璃料、低膨胀系数的陶瓷料、有机流延体系三部分组成，其中的低膨胀系数的玻璃料+陶瓷料，按照100％计量，有机流延体系是在玻璃料+陶瓷料100份基础上，以外加方式计算质量百分数；各组分的配比为：
低膨胀玻璃料25～70％；低膨胀陶瓷料30～75％；外加有机流延体系55～82％。
优选低膨胀系数的玻璃料组分和各组分占系数的玻璃料总量的重量百分含量分别为：
Li2O 5～10％；CaO 10～15％；MgO 4～8％；BaO 3～7％；SiO2 35～50％；B2O3 12～20％；Al2O3 1.0～8％；Na2O 0.5～5％；K2O 0.5～5％。
低膨胀系数陶瓷料为堇青石、莫来石、硅灰石或钛酸盐中的任意一种或多种，再加上氧化铝陶瓷；其中氧化铝陶瓷的质量占低膨胀系数陶瓷料总质量的8～12％。
优选外加有机流延体系由酒精与丁酮质量比为1：(1.3～1.5)的双溶剂、等质量比蓖麻油和聚丙烯酰胺双分散剂、聚乙烯缩丁醛粘结剂、邻苯二甲酸二丁酯增塑剂、异佛尔酮流平剂、乙二醇消泡剂六种成分组成，各成分占玻璃复合陶瓷细粉总重的重量百分含量分别为：
酒精+丁酮双溶剂45～70％；蓖麻油+聚丙烯酰胺等比例双分散剂1～4％；聚乙烯缩丁醛6～15％；邻苯二甲酸二丁酯2～5％；异佛尔酮0.1～2％；乙二醇0.3～3％。
本发明还提供了一种制备上述的宽频低膨胀系数低温共烧玻璃复合陶瓷的方法，其具体步骤如下：
(1)按锂钙镁硼铝硅酸盐系玻璃配方分别称取Li2O、CaO、MgO、BaO、SiO2、B2O3、Al2O3、Na2O和K2O，混合12～24h；
(2)锂钙镁硼铝硅酸盐系玻璃混合料放进坩埚，1320～1580℃保温3～10h使其完全熔化均匀，倒入蒸馏水，获得纯净透明玻璃渣；
(3)分别将碎玻璃渣，经球磨得到平均粒径为1.0～5.0μm的锂钙镁硼铝硅酸盐玻璃粉料；
(4)称取锂钙镁硼铝硅酸盐玻璃和陶瓷料混合，加入溶剂(酒精+丁酮)、分散剂(蓖麻油+聚丙烯酰胺)、粘结剂(聚乙烯缩丁醛)和增塑剂(邻苯二甲酸二丁酯)，球磨12～24h，经真空除泡后流延成型，自然干燥后，得到本发明所需的低膨胀系数玻璃陶瓷生料带；
(5)将生料带裁剪，印刷贵金属金或银浆料，热等静压叠合，置于温度场均匀的电热丝炉内，以1～2℃/min从室温升温至500～550℃，保温45～60min后，以5～10℃/min升温至650～920℃，保温10～60min，随炉冷却后，得到宽频低膨胀系数低温共烧玻璃复合陶瓷。
本发明宽频低膨胀系数低温共烧玻璃/陶瓷多层微电路基片材料的特点：
(1)流延所制备的生料带致密、生瓷带上下表面平整光滑，单层有效面积≥205×205mm2，单层厚度127um±3.5um,254um±5um,厚度按需可连续调节且厚度误差±3％可控；
(2)烧结温度较低，在650-920℃；
(3)烧成收缩率11.5～15.5％(X、Y轴)、15～25％(Z轴)，连续可调；与Au，Ag，铜低熔点金属浆料印刷，实现共烧匹配，如图1所示；
(4)烧结瓷体具有优异的介电性能：在10Mz-80GHz宽频范围，介电常数低4.0～20连续可调，介电损耗<0.0020；
(5)生料带烧结体晶粒细小、分布均匀，气孔率低、结构致密，如图2所示。
附图说明
图1为No.1多元玻璃/陶瓷流延生瓷带印刷微电路多层热等静压叠合基板照片；
图2为No.1低温850℃烧成玻璃-陶瓷体致密化微观结构SEM图。
具体实施方式
表1为本发明具体实施例中的锂钙镁硼铝硅酸盐系玻璃各组分含量。按表1所示分别称取各组分，经24h混匀后，在铂金坩埚内于1550℃保温5h使其完全熔融和均匀化，倒入蒸馏水中得到透明的锂钙镁硼铝硅酸盐系碎玻璃，将所得到的碎玻璃，经湿法球磨(用玛瑙球)得到平均粒径为3-5μm锂钙镁硼铝硅酸盐系玻璃粉料。
按表2的配方进行连续流延成型干燥后，得到本发明用低膨胀系数致密化的生料带。对生料带切割、打孔、印制电路、填孔，在70℃等静压下(3000psi)叠合多层、切割，No.1多元玻璃/陶瓷流延生瓷带印刷微电路多层热等静压叠合基板照片如图1所示。然后从室温以1-2℃/min升温到500℃，保温2h，以确保试样中的有机物充分排除，然后以5-7℃/min升温到850℃保温15-30min。对烧结体性能测试如表3所示。No.1低温850℃烧成玻璃-陶瓷体致密化微观结构SEM图如图2所示。
表2中加入溶剂为酒精+丁酮(质量比1:1.4)、分散剂为等比例蓖麻油+聚丙烯酰胺、粘结剂为聚乙烯缩丁醛和增塑剂为邻苯二甲酸二丁酯。
表1本发明中锂钙镁硼铝硅酸盐系典型玻璃各组分含量(wt％)
组分 <![CDATA[Li<sub>2</sub>O]]> CaO BaO MgO <![CDATA[SiO<sub>2</sub>]]> <![CDATA[B<sub>2</sub>O<sub>3</sub>]]> <![CDATA[Na<sub>2</sub>O]]> <![CDATA[K<sub>2</sub>O]]> <![CDATA[Al<sub>2</sub>O<sub>3</sub>]]>
No.1 5 11 3.5 4.5 47.9 18.5 2.5 2.6 4.5
No.2 5.5 13 3.5 4.5 46 15 3 3 6.5
No.3 6 15 3.5 5 43.5 12 2.5 3.5 9
表2宽频低损耗低膨胀系数玻璃/陶瓷流延生料带各组分的含量(wt％)
Figure BDA0002763908310000041
Figure BDA0002763908310000051
表3低温共烧玻璃复合陶瓷材料烧结收缩、热膨胀系数与高频介电性能
Figure BDA0002763908310000052

Claims (3)

1.一种宽频低膨胀系数低温共烧玻璃复合陶瓷，其特征是由玻璃复合陶瓷多层生料带及其印刷相应的贵金属浆料厚膜所组成；其中生料带中原料组分由低膨胀系数的玻璃料、低膨胀系数的陶瓷料、有机流延体系三部分组成，其中的低膨胀系数的玻璃料+陶瓷料，按照100％计量，有机流延体系是在玻璃料+陶瓷料100份基础上，以外加方式计算质量百分数；各组分的配比为：低膨胀玻璃料25～70％；低膨胀陶瓷料30～75％；外加有机流延体系55～82％；其中低膨胀系数的玻璃料组分和各组分占系数的玻璃料总量的重量百分含量分别为：Li2O 5～10％；CaO 10～15％；MgO 4～8％；BaO 3～7％；SiO2 35～50％；B2O3 12～20％；Al2O3 1.0～8％；Na2O 0.5～5％；K2O 0.5～5％；低膨胀系数陶瓷料为堇青石、莫来石、硅灰石或钛酸盐中的任意一种或多种，再加上氧化铝陶瓷；其中氧化铝陶瓷的质量占低膨胀系数陶瓷料总质量的8～12％；外加有机流延体系由酒精与丁酮质量比为1：(1.3～1.5)的双溶剂、等质量比的蓖麻油和聚丙烯酰胺双分散剂、聚乙烯缩丁醛粘结剂、邻苯二甲酸二丁酯增塑剂、异佛尔酮流平剂、乙二醇消泡剂六种成分组成。
2.根据权利要求1所述的宽频低膨胀系数低温共烧玻璃复合陶瓷，其特征是外加有机流延体系各成分占玻璃复合陶瓷细粉总重的重量百分含量分别为：
酒精+丁酮双溶剂45～70％；蓖麻油+聚丙烯酰胺等质量比双分散剂1～4％；聚乙烯缩丁醛6～15％；邻苯二甲酸二丁酯2～5％；异佛尔酮0.1～2％；乙二醇0.3～3％。
3.一种制备如权利要求1所述的宽频低膨胀系数低温共烧玻璃复合陶瓷的方法，其具体步骤如下：
(1)按锂钙镁硼铝硅酸盐系玻璃配方分别称取Li2O、CaO、MgO、BaO、SiO2、B2O3、Al2O3、Na2O和K2O，混合12～24h；
(2)锂钙镁硼铝硅酸盐系玻璃混合料放进坩埚，1320～1580℃保温3～10h使其完全熔化均匀，倒入蒸馏水，获得纯净透明玻璃渣；
(3)分别将碎玻璃渣，经球磨得到平均粒径为1.0～5.0μm的锂钙镁硼铝硅酸盐玻璃粉料；
(4)称取锂钙镁硼铝硅酸盐玻璃和陶瓷料混合，加入溶剂、分散剂、粘结剂和增塑剂，球磨12～24h，经真空除泡后流延成型，自然干燥后，得到低膨胀系数玻璃陶瓷生料带；
(5)将生料带裁剪，印刷贵金属金或银浆料，热等静压叠合，置于温度场均匀的电热丝炉内，以1～2℃/min从室温升温至500～550℃，保温45～60min后，以5～10℃/min升温至650～920℃，保温10～60min，随炉冷却后，得到宽频低膨胀系数低温共烧玻璃复合陶瓷。
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