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CN114573333B - 一种低介电硅灰石系低温共烧陶瓷材料及其制备方法 - Google Patents

一种低介电硅灰石系低温共烧陶瓷材料及其制备方法 Download PDF

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CN114573333B
CN114573333B CN202210188646.1A CN202210188646A CN114573333B CN 114573333 B CN114573333 B CN 114573333B CN 202210188646 A CN202210188646 A CN 202210188646A CN 114573333 B CN114573333 B CN 114573333B
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low
temperature
ceramic material
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CN114573333A (zh
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李进
余祖高
谭金刚
石珊
陆建军
童建喜
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Jiaxing Glead Electronics Co ltd
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Jiaxing Glead Electronics Co ltd
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Priority to CN202210188646.1A priority Critical patent/CN114573333B/zh
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Priority to JP2023574632A priority patent/JP2024520706A/ja
Priority to US18/562,338 priority patent/US20240246863A1/en
Priority to PCT/CN2022/114695 priority patent/WO2023159895A1/zh
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Abstract

本发明公开一种低介电硅灰石系低温共烧陶瓷材料及其制备方法，涉及电子材料技术领域。该陶瓷材料配方组成为：CaxSiO3+awt％SiO2+bwt％R2O+cwt％Bi2O3+dwt％B2O3+ewt％MO；其中:0.9≤x≤1.1,0<a≤30,1≤b≤5,0<c≤3,0<d≤6,0≤e≤10；R2O为Li2O、K2O中的至少一种；MO为ZnO、MgO、BaO、CoO、CuO、La2O3、MnO2中的一种或多种。本发明提供的低温共烧陶瓷材料满足低介电、低损耗及低温烧结的要求，可应用于毫米波LTCC器件等领域。

Description

一种低介电硅灰石系低温共烧陶瓷材料及其制备方法
技术领域
本发明属于电子材料技术领域，具体涉及一种低介电硅灰石系低温共烧陶瓷材料及其制备方法。
背景技术
低温共烧陶瓷技术(Low-temperature co-firing ceramics，LTCC)是电子封装技术的一种，其包括低温共烧陶瓷材料、器件设计等技术，其中低温共烧陶瓷是基础和关键。近年来，随着5G通信技术的快速发展，微波技术朝着更高频率，即向着毫米波和亚毫米波的方向发展，也对低温共烧陶瓷材料提出越来越高的要求，其中包括：低介电常数，以降低信号在传输过程中的延迟时间；高Q值(1/tanδ)，即低介电损耗，以降低器件的插入损耗，保证良好的选频特性；能够在900℃下与Ag、Cu等金属导电材料实现共烧；除此之外，还应具有足够的机械强度以及环境可靠性等性能，具备抗电镀或化学镀镀液侵蚀性。
目前研究的高频低介电常数低温共烧陶瓷材料主要有微晶玻璃、玻璃-陶瓷和陶瓷-助剂三大体系。其中微晶玻璃体系在烧结过程需要严格控制材料的析晶问题，对工艺过程要求较为严苛，目前只有美国FEERO公司的A6M材料得到广泛应用。玻璃-陶瓷体系需要较多玻璃才能实现陶瓷的低温烧结，但带来的问题却是材料损耗的急剧增大。而陶瓷-助剂体系的材料一般很难达到较低的介电常数，不像玻璃-陶瓷体系中可引入较低介电常数的玻璃。
(Ca,Mg)SiO3系微波介质陶瓷具有良好的介电性能，材料成本低廉。专利CN103193389B中混合至少两种氧化镁、氧化钙或氧化硅在1500-1800℃下形成玻璃态，且氧化镁、氧化钙及氧化硅的总量为100摩尔百分比，然后添加CaTiO3、MgTiO3、ZrTiO4及TiO2等材料在1500-1800℃下熔融后再在900℃下烧结。此方法过程复杂，而且介电常数较高，两次熔融至玻璃态的过程导致其Q×f值较低。专利申请CN112759378A中介绍了一种CaO-MgO-TiO2-SiO2陶瓷材料，该材料将碳酸钙、氧化镁、二氧化钛、二氧化硅、氧化锰、氧化锂和氧化铋混合后直接预烧然后再860-880℃烧结而成的低温共烧陶瓷。其中氧化锂和氧化铋作为烧结助剂复合加入配料中，其和TiO2组合形成低共熔点的物质Li2TiO3(900℃)。此方法在预烧过程中加入所有原料，会导致预烧时各成分之间的反应不可控，生成的物相复杂且具有不确定性。而且其材料介电常数介电常数为9.5±0.1,Q×f值较低。以上专利所述材料的介电常数都超过9，限制了其在低介高频场景的应用。专利CN 200410039848.1报道了以(Ca,Mg)SiO3系统为主成分，采用CaTiO3调整频率温度系数，Li2CO3和V2O5为烧结助剂的低温烧结微波介质陶瓷配方及制备工艺，该低温烧结微波介质陶瓷材料可与银电极实现良好共烧匹配，其材料性能：介电常数8-10，品质因数Qf>25000GHz，该材料取得了批量应用。但该材料存在以下问题：(1)低熔点氧化物V2O5具有极佳的助烧效果，可显著降低(Ca,Mg)SiO3陶瓷的烧结温度，但其具有较强的毒性，对人体有害，不能满足日益重视的环保需要。(2)V2O5在烧结过程中形成液相促进陶瓷烧结的同时，也易促使银电极的短距离扩散，易发生银迁移造成的层间电路短路风险，这将造成产品可靠性不良的重大隐患。
发明内容
为了解决上述技术问题，本发明的第一个目的在于提供一种低介电硅灰石系低温共烧陶瓷材料，该材料具有较低的介电常数，较高的Q×f值，较低的频率温度系数，而且能够实现低温烧结。本发明的第二个目的在于提供一种低介电硅灰石系低温共烧陶瓷材料及其制备方法，采用先合成主相陶瓷，再制备氧化物助烧剂，最后进行低温烧结的合成路线。该制备方法烧结工艺简单，可重复性好。
为了实现上述第一个发明的目的，本发明采用以下技术方案：
一种低介电硅灰石系低温共烧陶瓷材料，该低温共烧陶瓷材料的配方表达式为：CaxSiO3+awt％SiO2+bwt％R2O+cwt％Bi2O3+dwt％B2O3+ewt％MO；其中:
主相陶瓷材料的组成为：CaxSiO3，且0.9≤x＜1.0。
0<a≤30,1≤b≤5,0<c≤3,0<d≤6,0<e≤10；a、b、c、d和e分别为SiO2、R2O、Bi2O3、B2O3和MO相占CaxSiO3的质量分数；
R2O为Li2O、K2O中的至少一种；
MO为ZnO、MgO、BaO、CoO、CuO、La2O3、MnO2中的一种或多种；
SiO2为石英和熔融石英中的至少一种。
作为优选方案，所述SiO2为熔融石英。
为了实现上述第二个发明的目的，本发明采用以下技术方案：
一种低介电硅灰石系低温共烧陶瓷材料的制备方法，其特征在于，包括以下步骤：
1)主相陶瓷CaxSiO3的合成：按化学式CaxSiO3计量比称量原材料CaCO3和SiO2，以去离子水为溶剂，球磨混合16～24h后干燥再过40目筛，粉碎均匀后装入氧化铝坩埚在900℃～1300℃下煅烧2～4h合成主相陶瓷，研磨后作为陶瓷基料备用；
2)烧结助剂的合成：按bwt％R2O+cwt％Bi2O3+dwt％B2O3+ewt％MO的相对质量分数比，称取Li2CO3、K2CO3、Bi2O3、B2O3或H3BO3、ZnO、MgO或Mg(OH)2、BaCO3、CoO或Co2O3、CuO、La2O3、MnO2或MnCO3原料，按混合料与无水乙醇的质量比1：1～1.5加入乙醇，采用湿法混料16-24h后于80℃烘干，将烘干的混合料过40目筛，装入氧化铝坩埚，在500-700℃下煅烧2-4h，研磨后作为烧结助剂备用；其中1≤b≤5,0<c≤3,0<d≤6,0＜e≤10，b、c、d和e分别为R2O、Bi2O3、B2O3和MO相占CaxSiO3的质量分数；
3)制备好的主相CaxSiO3陶瓷、SiO2和氧化物助烧剂按CaxSiO3+awt％SiO2+bwt％R2O+cwt％Bi2O3+dwt％B2O3+ewt％MO的质量配比进行混合，以ZrO2球为磨介，以乙醇为溶剂，球磨混料16～24h后干燥，加入重量含量为5％～8％的聚乙烯醇粘合剂研磨造粒，过筛后在80～120MPa压力下压制成直径20mm，厚度10mm的坯体，在850℃～950℃空气气氛下烧结1～3h，即得到所述低介电硅灰石系低温共烧陶瓷材料，其中a、b、c、d和e分别为SiO2、R2O、Bi2O3、B2O3和MO相占CaxSiO3的质量分数。
与现有技术相比，本发明材料具有以下优势：
1.本发明提供一种简单、可靠和低成本的制备方法。采用主相陶瓷和烧结助剂分别合成，然后制备低温共烧陶瓷的路线。此方法确保主相陶瓷物相的成分可控，另外确保烧结助剂合成较低共熔点(低于700℃)的Li2O(K2O)-Bi2O3-B2O3等化合物。对比现有技术，此方法合成的主相陶瓷物相更易可控，低共熔点化合物的降温效果更好，且介电性能更好。
2.本专利对主相陶瓷的钙硅比进行了设计和优化，研究其对材料介电性能的影响。特别地，当主相陶瓷CaxSiO3中的0.9≤x＜1，材料的介电性能较优。这是由于预烧过程中除了生成硅灰石相(CaSiO3)，还有部分介电损耗较大的Ca2SiO4相生成，因此过量SiO2的有利于促进硅灰石相的合成，同时也提高了材料的介电性能。
3.使用熔融石英和CaxSiO3陶瓷进行复合，一方面熔融石英的介电常数较小，可以有效降低材料的介电常数；另一方面熔融石英在烧结过程中易形成液相，因此能起到湿润粉体颗粒，促进烧结的效果。
4.本发明通过引入复合氧化物进行协同降温，并控制碱金属氧化物和Bi2O3的添加量，规避了陶瓷材料与银电极共烧时极易发生的由于银迁移造成的层间电路短路风险。另外为了规避复杂且难以控制批次稳定性的玻璃助剂制备工艺，通过对引入的各种烧结助剂氧化物进行预先混料煅烧处理工艺，解决了陶瓷流延浆料制备时B2O3等氧化物以及粉体中的自由羟基与PVB等粘合剂中的羟基交联反应导致浆料粘度偏大而无法得到高质量生瓷片的问题。
5.本发明提供一种低介电硅灰石系低温共烧陶瓷材料，其介电常数小于7.5，Q×f值大于20000GHz，频率温度系数绝对值小于35ppm/℃。满足毫米波器件要求的低介电常数和低损耗及较低频率温度系数的要求。
附图说明
构成本申请的一部分的说明书附图用来提供对本申请的进一步理解，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的限定。
图1是实施例2中陶瓷的XRD分析图谱；
图2是实施例4烧陶瓷样品的SEM扫描电镜图。
具体实施方式
下面详细描述本发明的实施例，所述实施例的示例在附图中示出，下面通过参考附图描述的实施例是示例的，旨在用于解释本发明，而不能理解为对本发明的限制。
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图和实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用以限定本发明。
实施例1
1)主相合成：按化学式Ca0.98SiO3计量比称量原材料CaCO3和石英，以去离子水为溶剂，球磨混合24h后干燥在过40目筛，粉碎均匀后装入氧化铝坩埚在1200℃下煅烧3h合成主相陶瓷。
2)烧结助剂的合成：按3wt％Li2O+2wt％Bi2O3+3wt％B2O3+3wt％ZnO的相对主相陶瓷的质量分数比，称取Li2CO3、Bi2O3、H3BO3、ZnO等原料，按混合料与无水乙醇的质量比1：1加入乙醇，采用湿法混料16h后于80℃烘干，将烘干的混合料过40目筛，装入氧化铝坩埚，在600℃下煅烧3h，研磨后作为烧结助剂备用。
3)在主相Ca0.98SiO3陶瓷中加入分别占主相陶瓷质量百分比为3.0wt％的熔融石英和上一步合成的烧结助剂进行混合，以ZrO2球为磨介，以乙醇为溶剂，球磨混料16h后干燥，加入重量含量8％的聚乙烯醇粘合剂研磨造粒，过筛后在100MPa压力下压制成直径20mm，厚度10mm的坯体。在850℃空气气氛下烧结3h，即得到低温共烧陶瓷材料并测试其介电性能。
实施例2
1)主相合成：按化学式CaSiO3计量比称量原材料CaCO3和石英，以去离子水为溶剂，球磨混合24h后干燥在过40目筛，粉碎均匀后装入氧化铝坩埚在1250℃下煅烧3h合成主相陶瓷。
2)烧结助剂的合成：按1.5wt％Li2O+1wt％K2O+0.5wt％Bi2O3+2.5wt％B2O3+3wt％BaO+2wt％MnO2的相对主相陶瓷的质量分数比，称取Li2CO3、K2CO3、Bi2O3、H3BO3、BaCO3、MnO2等原料，按混合料与无水乙醇的质量比1：1加入乙醇，采用湿法混料16h后于80℃烘干，将烘干的混合料过40目筛，装入氧化铝坩埚，在650℃下煅烧3h，研磨后作为烧结助剂备用。
3)在主相CaSiO3陶瓷中加入分别占主相陶瓷质量百分比为3.5wt％的熔融石英和上一步合成的烧结助剂进行混合，以ZrO2球为磨介，以乙醇为溶剂，球磨混料16h后干燥，加入重量含量8％的聚乙烯醇粘合剂研磨造粒，过筛后在100MPa压力下压制成直径20mm，厚度10mm的坯体。在900℃空气气氛下烧结3h即得到低温共烧陶瓷材料并测试其介电性能。图1为烧结后陶瓷的XRD图谱，陶瓷的主要物相为CaSiO3和少量的SiO2相。
实施例3
1)主相合成：按化学式Ca1.02SiO3计量比称量原材料CaCO3和石英，以去离子水为溶剂，球磨混合24h后干燥在过40目筛，粉碎均匀后装入氧化铝坩埚在1300℃下煅烧3h合成主相陶瓷。
2)烧结助剂的合成：按2.5wt％Li2O+1wt％Bi2O3+2.5wt％B2O3+2wt％MgO的相对主相陶瓷的质量分数比，称取Li2CO3、Bi2O3、H3BO3、MgO等原料，按混合料与无水乙醇的质量比1：1加入乙醇，采用湿法混料16h后于80℃烘干，将烘干的混合料过40目筛，装入氧化铝坩埚，在700℃下煅烧3h，研磨后作为烧结助剂备用。
3)在主相Ca1.02SiO3陶瓷中加入分别占主相陶瓷质量百分比为5.0wt％的熔融石英和上一步合成的烧结助剂进行混合，以ZrO2球为磨介，以乙醇为溶剂，球磨混料16h后干燥，加入重量含量8％的聚乙烯醇粘合剂研磨造粒，过筛后在100MPa压力下压制成直径20mm，厚度10mm的坯体。在850℃空气气氛下烧结3h，即得到低温共烧陶瓷材料并测试其介电性能。
实施例4
1)主相合成：按化学式CaSiO3计量比称量原材料CaCO3和石英，以去离子水为溶剂，球磨混合24h后干燥在过40目筛，粉碎均匀后装入氧化铝坩埚在1200℃下煅烧3h合成主相陶瓷。
2)烧结助剂的合成：按4wt％Li2O+1.5wt％Bi2O3+4wt％B2O3+1wt％La2O3+2wt％CuO的相对主相陶瓷的质量分数比，称取Li2CO3、Bi2O3、H3BO3、La2O3、CuO等原料，按混合料与无水乙醇的质量比1：1加入乙醇，采用湿法混料16h后于80℃烘干，将烘干的混合料过40目筛，装入氧化铝坩埚，在600℃下煅烧3h，研磨后作为烧结助剂备用。
3)在主相CaSiO3陶瓷中加入分别占主相陶瓷质量百分比为2.0wt％的熔融石英和上一步合成的烧结助剂进行混合，以ZrO2球为磨介，以乙醇为溶剂，球磨混料16h后干燥，加入重量含量8％的聚乙烯醇粘合剂研磨造粒，过筛后在100MPa压力下压制成直径20mm，厚度10mm的坯体。在880℃空气气氛下烧结3h即得到低温共烧陶瓷材料并测试其介电性能。图2为陶瓷样品截面的扫描电镜照片，可以看出这种低温共烧陶瓷的致密性较好。
实施例5
1)主相合成：按化学式Ca0.95SiO3计量比称量原材料CaCO3和熔融石英，以去离子水为溶剂，球磨混合24h后干燥在过40目筛，粉碎均匀后装入氧化铝坩埚在1100℃下煅烧3h合成主相陶瓷。
2)烧结助剂的合成：按3.75wt％Li2O+2.5wt％Bi2O3+3.75wt％B2O3+1wt％CoO+2wt％CuO的相对主相陶瓷的质量分数比，称取Li2CO3、Bi2O3、H3BO3、CoO、CuO等原料，按混合料与无水乙醇的质量比1：1加入乙醇，采用湿法混料16h后于80℃烘干，将烘干的混合料过40目筛，装入氧化铝坩埚，在650℃下煅烧3h，研磨后作为烧结助剂备用。
3)在主相Ca0.95SiO3陶瓷中加入分别占主相陶瓷质量百分比为10.0wt％的熔融石英和上一步合成的烧结助剂进行混合，以ZrO2球为磨介，以乙醇为溶剂，球磨混料16h后干燥，加入重量含量8％的聚乙烯醇粘合剂研磨造粒，过筛后在100MPa压力下压制成直径20mm，厚度10mm的坯体。在850℃空气气氛下烧结3h即得到低温共烧陶瓷材料并测试其介电性能。
实施例6
在实施例5中合成的主相Ca0.95SiO3陶瓷中加入主相陶瓷质量百分比为10.0wt％的石英和实施例5中合成的烧结助剂进行混合，以ZrO2球为磨介，以乙醇为溶剂，球磨混料16h后干燥，加入重量含量8％的聚乙烯醇粘合剂研磨造粒，过筛后在100MPa压力下压制成直径20mm，厚度10mm的坯体。在880℃空气气氛下烧结3h即得到低温共烧陶瓷材料并测试其介电性能。
实施例7
在实施例2中合成的主相CaSiO3陶瓷中加入主相陶瓷质量百分比为7.0wt％的熔融石英和实施例2中合成的烧结助剂进行混合，以ZrO2球为磨介，以乙醇为溶剂，球磨混料16h后干燥，加入重量含量8％的聚乙烯醇粘合剂研磨造粒，过筛后在100MPa压力下压制成直径20mm，厚度10mm的坯体。在850℃空气气氛下烧结3h即得到低温共烧陶瓷材料并测试其介电性能。
对照例1
将实施例2中合成的主相CaSiO3陶瓷和实施例2中合成的烧结助剂进行混合，以ZrO2球为磨介，以乙醇为溶剂，球磨混料16h后干燥，加入重量含量8％的聚乙烯醇粘合剂研磨造粒，过筛后在100MPa压力下压制成直径20mm，厚度10mm的坯体。在930℃空气气氛下烧结3h即得到低温共烧陶瓷材料并测试其介电性能。
表1是对照例与实施例1～7对应的材料介电性能测试结果。其中，介电性能采用Agilent 8719ET网络分析仪测试介电常数εr和Q×f值。样品的频率温度系数τf＝(f110-f25)/(f25×85)计算确定，其中f110和f25分别为样品在110℃和25℃下的谐振中心频率。
表1各实施例和对照例的介电性能测试结果
编号 εr Q×f(GHz) τf(ppm/℃)
1 6.68 24200 -25.9
2 6.85 22400 -30.3
3 7.26 21600 -34.8
4 6.92 22870 -28.6
5 6.40 21730 -23.7
6 6.45 20350 -25.2
7 6.60 20900 -27.5
对照例1 7.04 18580 -38.2
上表里列出的低温共烧陶瓷材料，其介电常数小于7.5，Q×f值大于20000GHz，频率温度系数绝对值小于35ppm/℃。满足毫米波器件要求的低介电常数和低损耗及较低频率温度系数的要求。与对照例相比，引入熔融石英后既能降低烧结温度，也能提高材料Q×f值和改善频率温度系数。
需要说明的是，在本发明的描述中，术语“包括”、“包含”等意在涵盖非排他性的包含，还包括一些没有明确列出的其他要素的过程、方法和原物料等。“实施例”或某个“具体实施例”等意指结合该实施例描述的具体特征、结构、材料或特点包含于本发明的至少一个实施例中。
因此，尽管上文已经应用了具体实施例对发明进行阐述，可以理解的是，上述实施例是用于理解本发明的方法及核心事项，不能理解为对本发明的限制。本领域的普通技术人员在不脱离本发明的原理和宗旨的情况下在本发明的范围内可以对上述实施例进行变化、修改、替换和变型，凡是依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均应视为本发明的保护范围。

Claims (2)

1.一种低介电硅灰石系低温共烧陶瓷材料，其特征在于，该低温共烧陶瓷材料的配方表达式为：CaxSiO3+awt％SiO2+bwt％R2O+cwt％Bi2O3+dwt％B2O3+ewt％MO；其中:
主相陶瓷材料的组成为：CaxSiO3，且0.9≤x＜1.0；
0<a≤30,1≤b≤5,0<c≤3,0<d≤6,0<e≤10；a、b、c、d和e分别为SiO2、R2O、Bi2O3、B2O3和MO相占CaxSiO3的质量分数；
R2O为Li2O、K2O中的至少一种；
MO为ZnO、MgO、BaO、CoO、CuO、La2O3、MnO2中的一种或多种；
SiO2为石英和熔融石英中的至少一种；
制备方法包括以下步骤：
1)主相陶瓷CaxSiO3的合成：按化学式CaxSiO3计量比称量原材料CaCO3和SiO2，以去离子水为溶剂，球磨混合16～24h后干燥再过40目筛，粉碎均匀后装入氧化铝坩埚在900℃～1300℃下煅烧2～4h合成主相陶瓷，研磨后作为陶瓷基料备用；
2)烧结助剂的合成：按bwt％R2O+cwt％Bi2O3+dwt％B2O3+ewt％MO的相对质量分数比，称取Li2CO3、K2CO3、Bi2O3、B2O3或H3BO3、ZnO、MgO或Mg(OH)2、BaCO3、CoO或Co2O3、CuO、La2O3、MnO2或MnCO3原料，按混合料与无水乙醇的质量比1：1～1.5加入乙醇，采用湿法混料16-24h后于80℃烘干，将烘干的混合料过40目筛，装入氧化铝坩埚，在500-700℃下煅烧2-4h，研磨后作为烧结助剂备用；其中1≤b≤5,0<c≤3,0<d≤6,0<e≤10，b、c、d和e分别为R2O、Bi2O3、B2O3和MO相占CaxSiO3的质量分数；
3)制备好的主相CaxSiO3陶瓷、SiO2和氧化物助烧剂按CaxSiO3+awt％SiO2+bwt％R2O+cwt％Bi2O3+dwt％B2O3+ewt％MO的质量配比进行混合，以ZrO2球为磨介，以乙醇为溶剂，球磨混料16～24h后干燥，加入重量含量为5％～8％的聚乙烯醇粘合剂研磨造粒，过筛后在80～120MPa压力下压制成直径20mm，厚度10mm的坯体，在850℃～950℃空气气氛下烧结1～3h，即得到所述低介电硅灰石系低温共烧陶瓷材料，其中a、b、c、d和e分别为SiO2、R2O、Bi2O3、B2O3和MO相占CaxSiO3的质量分数。
2.根据权利要求1所述的一种低介电硅灰石系低温共烧陶瓷材料，其特征在于，所述SiO2为熔融石英。
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