CN106747412B - 一种Ti基LTCC微波介电陶瓷材料及其制备方法 - Google Patents

一种Ti基LTCC微波介电陶瓷材料及其制备方法 Download PDF

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CN106747412B
CN106747412B CN201611149340.6A CN201611149340A CN106747412B CN 106747412 B CN106747412 B CN 106747412B CN 201611149340 A CN201611149340 A CN 201611149340A CN 106747412 B CN106747412 B CN 106747412B
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苏桦
王海宇
唐晓莉
张怀武
荆玉兰
李元勋
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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材料及其制造领域，具体涉及一种Ti基LTCC微波介电陶瓷材料及其制备方法。本发明首先将(Mg0.95Co0.05)2TiO4与Li2TiO3进行复合，然后再借助LMZBS玻璃掺杂助熔来实现整个材料体系的900～950℃低温烧结。最终实现在900℃低温烧结下最佳性能可达到介电常数：εr＝16.6,Q×f＝125800GHz，τf＝1.4ppm/℃。本发明兼具超低损耗、近零谐振频率温度系数以及低温烧结的高性能，其介电常数εr为16.6～17.1，Q×f值为88400～125800GHz，谐振频率温度系数τf为1.3～5.1ppm/℃。可广泛应用于LTCC微波基板、叠层微波器件和模块中。

Description

一种Ti基LTCC微波介电陶瓷材料及其制备方法
技术领域
本发明属于电子陶瓷材料及其制造领域，具体涉及一种具有超低损耗和近零谐振频率温度系数特性的Ti基LTCC微波介电陶瓷材料及其制备方法。
背景技术
LTCC(低温共烧陶瓷)技术是目前最为重要的无源集成以及有源/无源混合集成的技术，在当代电子整机系统中有着非常广泛的应用。LTCC技术的核心包括了三大部分，分别是LTCC工艺技术、LTCC设计技术和LTCC材料技术。其中LTCC材料技术最为关键。但目前国际上商用化的高性能LTCC材料主要都被美国、日本和德国的几家大公司所垄断，国内在此领域始终未能取得关键性技术突破，一方面导致我国研发的LTCC集成器件和组件成本较高，不利于相应产品的应用和推广；另一方面由于在核心材料技术上受制于人，也严重阻碍了我国LTCC产业的发展。因此，开发拥有自主知识产权的高性能LTCC材料迫在眉睫。
LTCC微波介电陶瓷材料是LTCC材料中应用最为广泛的一个分支。一般的微波介电陶瓷材料烧结温度都在1100℃以上，但为了与LTCC工艺(烧结温度为800℃～950℃)兼容，需将其烧结温度降低到950℃以下。常采用的方法主要包括添加低熔氧化物或玻璃助烧、引入化学合成方法以及采用超细粉体做原料等等；后两种方法成本高昂、并有一定的工艺局限性，因而添加低熔氧化物或玻璃助熔是目前实现LTCC微波介电陶瓷材料的主要方法。但即便采取这种方法，目前许多微波介电陶瓷材料的烧结温度都太高，比较难实现低温烧结，其次，过多低熔氧化物或玻璃的掺入，也会对材料的损耗性能构成很大的影响，导致Q×f下降很大。并且常用的低熔氧化物B2O3及V2O5，会在LTCC工艺后期流延过程中易导致浆料粘度过大而不稳定，限制了其实际应用。因此，选择适宜的LTCC材料体系和降温的途径非常重要，是获得高性能LTCC材料的关键。此外，为了使LTCC材料能更好的应用在LTCC集成器件和组件中，对其谐振频率温度系数的要求也越来越高，即要求其介电性能随温度的变化应尽可能的小，这样才能更好的保证LTCC集成器件和组件性能的温度稳定性。
近年来有研究报道(Mg0.95Co0.05)2TiO4体系材料具有很优良的微波介电性能，εr＝15.7,Q×f可高达280000GHz。但其烧结温度达到了1390℃，且其谐振频率温度系数τf在-52.5ppm/℃左右，温度稳定性较差，因此还不太适合于制备微波器件，也更不适合于应用到LTCC技术中。(Cheng-Liang Huang,Jhih-Yong Chen,High-Q Microwave Dielectrics inthe(Mg1-xCox)2TiO4Ceramics,J.Am.Ceram.Soc.,92,379–383(2009))。此后，该课题组采用复合SrTiO3的方法来调节(Mg0.95Co0.05)2TiO4材料的温度系数τf，在1300℃烧结温度下得到了微波损耗低且温度系数也很好的陶瓷材料：εr＝18.44,Q×f＝102200GHz，τf＝1.1ppm/℃。(Cheng-Liang Huang,Jhih-Yong Chen,Low-loss microwave dielectrics usingSrTiO 3–modified(Mg 0.95Co 0.05)2TiO 4ceramics，Journal of Alloys and Compounds485(2009)706–710))。但是，该陶瓷材料体系的烧结温度仍然太高，无法与LTCC技术兼容。并且由于许多种常规低熔助烧剂在(Mg0.95Co0.05)2TiO4材料中的降温效果都不理想，目前还没有任何实现(Mg0.95Co0.05)2TiO4材料900℃低温烧结的报道。
发明内容
针对上述存在问题或不足，本发明提供了一种Ti基LTCC微波介电陶瓷材料及其制备方法，最终生成的复合材料体系的晶相包括主晶相(Mg,Co)2TiO4，次晶相Li2TiO3以及另相(Mg,Co)TiO3(如图2所示)。
该Ti基LTCC微波介电陶瓷材料，由基料和助熔剂通过固相反应制得。先由(Mg0.95Co0.05)2TiO4和Li2TiO3两种原料按重量百分比43～44％：57～56％混合配得基料，然后掺入占基料重量百分比0.5～2wt％的LMZBS玻璃助熔剂，再通过固相反应制得。
所述(Mg0.95Co0.05)2TiO4其原料组成按照摩尔比为MgCO3：Co2O3：TiO2＝1.9：0.05：1；所述Li2TiO3其原料组成按照摩尔比为Li2CO3：TiO2＝1:1；
所述LMZBS助熔剂为Li2CO3-MgO-ZnO2-H3BO3-SiO2占基料重量百分比0.5～2wt％；其原料组成按摩尔比为Li2CO3:MgO:ZnO2:H3BO3：SiO2＝1-1.2:0.9-1.1:0.9-1.1:0.8-1:0.9-1.1。
本发明提供的上述以(Mg0.95Co0.05)2TiO4为主晶相的复合体系Ti基LTCC微波介电陶瓷材料，其烧结温度为900～950℃，介电常数εr为16.6～17.1，Q×f值为88400～125800GHz，谐振频率温度系数τf为1.3～5.1ppm/℃。可广泛应用于LTCC微波基板、叠层微波器件和模块中。
上述Ti基LTCC微波介电材料的制备方法如下：
步骤1、按照摩尔比MgCO3：Co2O3：TiO2＝1.9：0.05:1称料配制(Mg0.95Co0.05)2TiO4的原料；按照摩尔比Li2CO3：TiO2＝1:1称料配制Li2TiO3的原料；将配好的(Mg0.95Co0.05)2TiO4和Li2TiO3原料分别进行一次球磨混料均匀，再分别烘干备用；
步骤2、将步骤1所得的(Mg0.95Co0.05)2TiO4烘干料过筛后放入坩埚中压实，按2～3℃/分钟的升温速率升至1150～1200℃进行预烧，保温2～3小时，随炉冷却得到(Mg0.95Co0.05)2TiO4预烧料；将步骤1所得的Li2TiO3烘干料过筛后放入坩埚中压实，按2～3℃/分钟的升温速率升至800～850℃进行预烧，保温2～3小时，随炉冷却得到Li2TiO3预烧料；再将两种预烧料分别放入研钵中磨细备用；
步骤3、按摩尔比Li2CO3:MgO:ZnO2:H3BO3：SiO2＝1-1.2:0.9-1.1:0.9-1.1:0.8-1:0.9-1.1配料，然后湿混烘干后装入坩埚，按2～5℃/分在烧结炉中升温到1350～1400℃，保温2～4小时后直接从炉中取出倒入常温去离子水中淬冷得到LMZBS玻璃渣，然后将其烘干磨细得到LMZBS玻璃助熔剂；
步骤4、将步骤2制得的预烧料按照重量百分比(Mg0.95Co0.05)2TiO4：Li2TiO3＝43～44％：57～56％进行配料混合得到混合料，然后加入占混合料总质量百分比0.5～2wt％的步骤3所得助熔剂，三者一起于球磨机中进行二次球磨混合均匀，再烘干备用；
步骤5、将步骤4制得的粉料产物加入占其质量百分比为10％～30％的PVA溶液作为粘结剂，进行造粒并干压成型；
步骤6、将步骤5所得的产物放入烧结炉中，按2～3℃/分钟的升温速率升至250～350℃并保温2～3小时，再继续升温至500～550℃并保温2～4小时；然后再按2～4℃/分钟的升温速率升至900℃～950℃进行烧结，并保温2～4小时后，再按2～4℃/分钟的降温速率降至500～550℃，最后随炉冷却得到超低损耗LTCC微波介电陶瓷材料。
所述步骤5中PVA溶液的浓度为8～10％。
本发明首先将(Mg0.95Co0.05)2TiO4与Li2TiO3进行复合，一方面通过负温度系数的(Mg0.95Co0.05)2TiO4和正温度系数的Li2TiO3进行复合温度系数补偿，调节材料体系的温度系数到接近于零。另一方面通过具有更低烧结温度的Li2TiO3陶瓷的复合，将整个材料体系的烧结温度先适度降低。然后，再借助Li2CO3-MgO-ZnO2-H3BO3-SiO2(LMZBS)玻璃掺杂助熔来实现整个材料体系的900～950℃低温烧结。最终研发出的这种超低损耗LTCC微波介电陶瓷材料在900℃低温烧结下最佳性能可达到介电常数：εr＝16.6,Q×f＝125800GHz，τf＝1.4ppm/℃。该材料在LTCC集成器件和组件中很好的应用前景。
综上所述，本发明兼具超低损耗、近零谐振频率温度系数以及低温烧结的高性能，其介电常数εr为16.6～17.1，Q×f值为88400～125800GHz，谐振频率温度系数τf为1.3～5.1ppm/℃。可广泛应用于LTCC微波基板、叠层微波器件和模块中。
附图说明
图1为本发明的制备工艺流程示意图；
图2为实施例在900℃温度下烧结样品的XRD图谱。
具体实施方式
下面结合附图和具体实施例对本发明做进一步的详细说明，工艺方法如图1所示。
步骤1、按照摩尔比MgCO3：Co2O3：TiO2＝1.9：0.05:1称料配置(Mg0.95Co0.05)2TiO4；按照摩尔比Li2CO3：TiO2＝1:1称料配置Li2TiO3；将配好的(Mg0.95Co0.05)2TiO4和Li2TiO3分别进行一次球磨混料均匀，再分别烘干备用。
步骤2、将步骤1所得的(Mg0.95Co0.05)2TiO4烘干料过筛后放入坩埚中压实，按2℃/分钟的升温速率升至1200℃进行预烧，保温3小时，随炉冷却得到(Mg0.95Co0.05)2TiO4预烧料；将步骤1所得的Li2TiO3烘干料过筛后放入坩埚中压实，按2℃/分钟的升温速率升至850℃进行预烧，保温3小时，随炉冷却得到Li2TiO3预烧料。然后将两种预烧料分别放入研钵中磨细备用。
步骤3、按摩尔比Li2CO3:MgO:ZnO2:H3BO3：SiO2＝1:1:1:1:1配料，湿混烘干后装入坩埚，按3℃/分在烧结炉中升温到1350℃，保温3小时后直接从炉中取出倒入常温去离子水中淬冷得到LMZBS玻璃渣，然后将玻璃渣烘干磨细得到LMZBS玻璃助熔剂。
步骤4、将步骤2制得的(Mg0.95Co0.05)2TiO4和Li2TiO3预烧料按照重量百分比43％：57％进行配料混合，然后加入占混合料总重量百分比2wt％步骤3所得助熔剂，再将三者一起于球磨机中进行二次球磨混合均匀，再烘干备用。
步骤5、将步骤4制得的粉料产物加入占其质量百分比为20％的PVA熔液作为粘结剂，进行造粒并干压成型。PVA熔液的浓度为10％。
步骤6、将步骤5所得的生坯样品放入烧结炉中，按2℃/分钟的升温速率升至300℃并保温2小时，再继续升温至500℃并保温2小时；然后再按2℃/分钟的升温速率升至900℃～950℃进行烧结，并保温3小时，再按2℃/分钟的降温速率降至500℃，最后随炉冷却得到LTCC微波介电陶瓷材料。研制材料性能如表1所示。
表1
表1为不同烧结温度LMZBS玻璃掺杂量对材料体系微波介电性能的影响。
图2中表示掺杂2wt％LMZBS玻璃样品的XRD图谱；可以从图中看出有三种类型的特征峰，分别是(Mg,Co)2TiO4(+)，(Mg,Co)TiO3(*)和Li2TiO3(.)。掺杂LMZBS玻璃无特征峰，为非晶态。

Claims (4)

1.一种Ti基LTCC微波介电陶瓷材料，其特征在于：包括主晶相(Mg,Co)2TiO4，次晶相Li2TiO3以及另相(Mg,Co)TiO3三种不同的晶相，由基料和助熔剂通过固相反应制得；
其基料的原料组成为(Mg0.95Co0.05)2TiO4：Li2TiO3按重量百分比为43～44％：57～56％；所述(Mg0.95Co0.05)2TiO4其原料组成按照摩尔比为MgCO3：Co2O3：TiO2＝1.9：0.05：1；所述Li2TiO3其原料组成按照摩尔比为Li2CO3：TiO2＝1:1；
助熔剂为Li2CO3-MgO-ZnO2-H3BO3-SiO2即LMZBS玻璃，占总重量百分比为0.5～2wt％；其原料组成按摩尔比为Li2CO3:MgO:ZnO2:H3BO3：SiO2＝1-1.2:0.9-1.1:0.9-1.1:0.8-1:0.9-1.1。
2.如权利要求1所述Ti基LTCC微波介电陶瓷材料，其特征在于：烧结温度为900～950℃，介电常数16.6～17.1，Q×f值88400～125800GHz，谐振频率温度系数1.3～5.1ppm/℃。
3.如权利要求1所述Ti基LTCC微波介电陶瓷材料的制备方法，包括以下步骤：
步骤1、按照摩尔比MgCO3：Co2O3：TiO2＝1.9：0.05:1称料配置(Mg0.95Co0.05)2TiO4的原料；按照摩尔比Li2CO3：TiO2＝1:1称料配置Li2TiO3的原料；将配好的(Mg0.95Co0.05)2TiO4和Li2TiO3原料分别进行一次球磨混料均匀，再分别烘干备用；
步骤2、将步骤1所得的(Mg0.95Co0.05)2TiO4烘干料过筛后放入坩埚中压实，按2～3℃/分钟的升温速率升至1150～1200℃进行预烧，保温2～3小时，随炉冷却得到(Mg0.95Co0.05)2TiO4预烧料；将步骤1所得的Li2TiO3烘干料过筛后放入坩埚中压实，按2～3℃/分钟的升温速率升至800～850℃进行预烧，保温2～3小时，随炉冷却得到Li2TiO3预烧料；再将两种预烧料分别放入研钵中磨细备用；
步骤3、按摩尔比Li2CO3:MgO:ZnO2:H3BO3：SiO2＝1-1.2:0.9-1.1:0.9-1.1:0.8-1:0.9-1.1配料，然后湿混烘干后装入坩埚，按2～5℃/分在烧结炉中升温到1350～1400℃，保温2～4小时后直接从炉中取出倒入常温去离子水中淬冷得到LMZBS玻璃渣，然后将其烘干磨细得到LMZBS玻璃助熔剂；
步骤4、将步骤2制得的预烧料按照重量百分比(Mg0.95Co0.05)2TiO4：Li2TiO3＝43～44％：57～56％进行配料混合得到混合料，然后加入占混合料总质量百分比0.5～2wt％的步骤3所得助熔剂，三者一起于球磨机中进行二次球磨混合均匀，再烘干备用；
步骤5、将步骤4制得的粉料产物加入占其质量百分比为10％～30％的PVA溶液作为粘结剂，进行造粒并干压成型；
步骤6、将步骤5所得的产物放入烧结炉中，按2～3℃/分钟的升温速率升至250～350℃并保温2～3小时，再继续升温至500～550℃并保温2～4小时；然后再按2～4℃/分钟的升温速率升至900℃～950℃进行烧结，并保温2～4小时后，再按2～4℃/分钟的降温速率降至500～550℃，最后随炉冷却得到超低损耗LTCC微波介电陶瓷材料。
4.如权利要求3所述Ti基LTCC微波介电陶瓷材料的制备方法，其特征在于：所述步骤5中PVA溶液的浓度为8～10％。
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