CN110723965A - 一种无助熔剂ltcc微波陶瓷材料及其制备方法 - Google Patents
一种无助熔剂ltcc微波陶瓷材料及其制备方法 Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 47
- 239000000919 ceramic Substances 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 229910007270 Si2O6 Inorganic materials 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000012071 phase Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000005245 sintering Methods 0.000 claims description 22
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 10
- 229910052681 coesite Inorganic materials 0.000 claims description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims description 10
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052682 stishovite Inorganic materials 0.000 claims description 10
- 229910052905 tridymite Inorganic materials 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
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- 239000007790 solid phase Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 7
- 238000010327 methods by industry Methods 0.000 abstract description 2
- 230000008054 signal transmission Effects 0.000 abstract description 2
- 229910052637 diopside Inorganic materials 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 4
- 230000010354 integration Effects 0.000 description 3
- 238000009766 low-temperature sintering Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 239000004231 Riboflavin-5-Sodium Phosphate Substances 0.000 description 1
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- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
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- 229910052642 spodumene Inorganic materials 0.000 description 1
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Abstract
本发明属于电子陶瓷材料及其制造领域，涉及一种无助熔剂的LTCC微波陶瓷材料及其制备方法。本发明提供的LTCC微波陶瓷材料，低介低损耗，以CaMg1‑x‑yLi2xZnySi2O6为主晶相，0.1≤x≤0.3，0.1≤y≤0.3，于850℃～950℃烧结，介电常数εr6.9～7.8，品质因数Q×f值25000GHz～45800GHz，谐振频率温度系数τf为‑30～‑40ppm/℃，通过固相法制备。有效降低信号传输过程中的损耗和信号串扰风险，可广泛应用于LTCC微波基板、叠层微波器件和模块中；材料体系中未加入任何玻璃助熔剂，不仅降低了材料制备工艺和成本，而且更有利于提升材料的品质因数并减少因玻璃掺杂引起的LTCC工艺兼容性问题；生产原料便宜，工艺工程简单，方便操作并利于降低成本。
Description
技术领域
本发明属于电子陶瓷材料及其制造领域，涉及一种无助熔剂掺杂的低介低损耗LTCC微波陶瓷材料及其制备方法。
背景技术
随着通信、电脑及其周边产品和家用电器不断向高频化、数字化方向发展，对元器件的小型化、集成化、多功能化、模块化以及高可靠性要求愈来愈迫切。LTCC(低温共烧陶瓷)技术以其优异的电学、机械、热学及工艺特性，为无源器件以及无源/有源器件混合集成的发展创造了条件，并迅速在叠层片式无源器件中获得了广泛的应用，在国内外的高校、研究机构和公司等得到广泛的研发和生产，并成为了电子元器件小型化、片式化和集成化的首选方式。然而，为了获得高性能的LTCC器件，首先就需要开发出高性能的LTCC材料。国内目前企业和研究所所采用LTCC微波介电陶瓷材料，大部分还依赖于从日本、美国进口。因此，亟须开发出拥有自主知识产权的高性能LTCC微波介电陶瓷粉料，为研发LTCC小型集成化微波器件奠定材料基础。
LTCC微波陶瓷材料是LTCC材料中应用非常广泛的一个分支。其实现方式包括采用微晶玻璃法、玻璃-陶瓷复合法以及固相反应烧结法三大类。其中前两类都包含了大量的玻璃，虽然容易实现材料体系的低温烧结，但材料的介电损耗也都较高。而采用传统固相反应法烧结法制备陶瓷体系的LTCC微波材料，由于一般的微波陶瓷材料烧结温度都在1300℃以上，为了将其烧结温度降低到与LTCC工艺兼容(一般烧结温度为800℃～900℃之间)，常通过添加各种低熔玻璃或氧化物来实现材料体系的低温烧结。在这些低熔掺杂助熔方式中，一方面添加的低熔助烧剂容易恶化陶瓷基体微波介电性能，另外如果采用玻璃做助熔剂，制备玻璃的成本也较高。
CaMgSi2O6是一种属于斜辉石类的硅酸盐，在CaMgSi2O6晶体结构中，Ca2+占据八配位多面体，Mg2+占据较规则且更小的六配位八面体，CaO8多面体和MgO6八面体之间通过SiO4四面体连。CaMgSi2O6微波介电陶瓷具有较低的介电常数(～7.5)，是LTCC基板材料的重要候选材料之一。纯相CaMgSi2O6微波介电陶瓷需要较高的烧结温度(～1290℃)实现致密，其介电性能如下：εr＝7.46,Q×f＝59638GHz，τf＝-46ppm/℃。由此可见，CaMgSi2O6陶瓷有很好的潜质作为陶瓷基的高性能LTCC材料，但其烧结温度还太高，与LTCC工艺不兼容，一般需要通过直接加氧化物或玻璃将其烧结温度降到900℃。如H.Wang等人在"Effect ofB2O3additives on the sintering and dielectric behaviors of CaMgSi2O6ceramics",Journal of materials science and technology,2010,26(4):351–354中，添加6wt％的B2O3后，CaMgSi2O6微波介电陶瓷能在1100℃形成微观致密结构，同时介电常数εr＝7.61，tanδ＝7×10-4(1MHz)。该烧结温度离与LTCC工艺兼容的900℃还有一定距离。而T.Joseph等添加15wt％LBS玻璃的CaMgSi2O6微波介电陶瓷能在925℃下实现烧结，其微波介电性分别为：εr＝8.0,Q×f＝15000GHz(10.17GHz)，τf＝–49ppm/℃；而添加15wt％LMZBS的CaMgSi2O6微波介电陶瓷能在900℃下实现烧结，相对添加LBS，添加LMZBS玻璃的CaMgSi2O6微波介电陶瓷具有更好的微波介电性能，其εr＝8.2、Q×f＝32000GHz(10.15GHz)及τf＝–48ppm/℃("Effect of glass addition on the microwave dielectric properties ofCaMgSi2O6 ceramics",International Journal of Applied Ceramic Technology,2010,7(S1):E98–E106))。但添加玻璃助熔剂，不仅增加了材料制备的成本，而且也不太利于介电损耗的降低，同时存在引入玻璃导致后期LTCC工艺兼容性的问题。
发明内容
针对上述存在问题或不足，为解决现有硅酸盐陶瓷材料在LTCC技术应用上存在的成本相对较高以及后期流延工艺兼容的问题。本发明提供了一种无助熔剂的LTCC微波陶瓷材料，在不添加任何助熔剂的前提下就可实现900℃低温烧结，且制得的陶瓷材料低介低损，谐振频率温度系数τf为-30～-40ppm/℃。
该无助熔剂的LTCC微波陶瓷材料以CaMg1-x-yLi2xZnySi2O6为主晶相，0.1≤x≤0.3，0.1≤y≤0.3，烧结温度850℃～950℃，介电常数εr为6.9～7.8，品质因数Q×f值25000GHz～45800GHz，谐振频率温度系数τf为-30～-40ppm/℃。
由原料CaCO3、MgO、Li2CO3、ZnO和SiO2按摩尔比CaCO3：MgO：Li2CO3：ZnO：SiO2＝1:1-x-y:x:y:2配制，通过固相法制得。由于无助熔剂因此降低了成本，制备方法简单成熟，在作为LTCC微波介质基板或器件材料时，可以显著降低微波器件或模块的损耗。
其制备方法包括以下步骤：
步骤1、以CaCO3、MgO、Li2CO3、ZnO和SiO2为初始原料，按照CaMg1-x-yLi2xZnySi2O6，0.1≤x≤0.3，0.1≤y≤0.3的陶瓷配方分子式中各元素的摩尔比例折算出CaCO3、MgO、Li2CO3、ZnO和SiO2的质量百分比，进行称料、一次球磨、混料均匀后烘干；
步骤2、将步骤1所得的烘干料过筛后放入坩埚中压实，按1℃～2℃/分的升温速率升至850℃～950℃进行预烧，保温2～3小时，随炉自然冷却得到预烧料；
步骤3、将步骤2所得预烧料在球磨机中进行二次球磨；
步骤4、将步骤3所得到的二次球磨料烘干后，加入质量分数为10％～20％的PVA溶液进行造粒并干压成型；
步骤5、将步骤4所得的样品放入烧结炉中，按1℃～2℃/分的升温速率升至200℃～300℃保温1～2小时后，继续升温至500℃～600℃保温2～4小时，以排除生坯中的水分和胶水；然后再按2℃～5℃/分的升温速率升温至850℃～950℃进行烧结，保温2～3小时，再按2℃～5℃/分的降温速率降温至500℃～600℃，随后随炉自然冷却得到无助熔剂的低介低损耗微波陶瓷材料。
进一步的，所述步骤4中PVA溶液的浓度为8～10％。
经过以上方案的具体五个步骤，就可以制备得到本发明无助熔剂的低介低损耗LTCC微波陶瓷材料。经过测试，本发明提供的无助熔剂的低介低损耗LTCC微波陶瓷材料，其介电常数在6.9～7.8之间，品质因数Q×f值均在25000GHz以上、最高可达到45800GHz，谐振频率温度系数τf为-30～-40ppm/℃。
本发明提供的无助熔剂的低介低损耗LTCC微波陶瓷材料的优点在于：
1、介电常数在6.9～7.8之间，可广泛应用于LTCC微波基板、叠层微波器件和模块中。
2、具有极低的介电损耗，在900℃低温烧结时Q×f最高可达45800GHz，可以有效降低信号传输过程中的损耗和信号串扰风险。
3、材料体系中未加入任何玻璃助熔剂，不仅降低了材料制备工艺和成本，而且更有利于提升材料的品质因数并减少因玻璃掺杂引起的LTCC工艺兼容性问题。
4、生产原料便宜，工艺工程简单，方便操作并利于降低成本。
附图说明
图1为本发明的制备工艺流程示意图。
具体实施方式
下面结合具体制备实例，进一步说明本发明提供的无助熔剂低介低损耗LTCC微波陶瓷材料。
步骤1、以CaCO3、MgO、Li2CO3、ZnO、SiO2为初始原料，按照CaMg0.75Li0.2Zn0.15Si2O6(x＝0.1，y＝0.15时)陶瓷配方分子式中各元素的摩尔比例折算出CaCO3、MgO、Li2CO3、ZnO、SiO2的质量百分比，进行准确称料后，在行星球磨机中一次球磨12小时、混料均匀后放在100℃的烘箱中烘干24小时；
步骤2、将步骤1所得的烘干料过40目筛后放入坩埚中压实，按3℃/分的升温速率升至900℃进行预烧，保温3小时，随炉自然冷却得到预烧料备用；
步骤3、将步骤2所得的预烧料，在行星球磨机中进行二次球磨6小时，然后放在100℃的烘箱中烘干24小时；
步骤4、将步骤3所得到的二次球磨烘干料，加入质量分数为20％的PVA溶液(PVA浓度为10％)进行造粒，并干压成型为直径12mm、厚度6mm的圆柱型样品；
步骤5、将步骤4所得的样品放入烧结炉中，按2℃/分的升温速率缓慢升至300℃保温2小时，继续按2℃/分的速率升温至600℃保温3小时，以排除生坯中的水分和胶水；然后再按5℃/分的升温速率升温至900℃进行烧结，保温3小时，再按5℃/分的降温速率降温至600℃，随后随炉自然冷却得到无助熔剂的低介低损耗LTCC微波陶瓷材料。
以上具体实施方式所提供的无助熔剂的低介低损耗LTCC微波陶瓷材料，其介电常数约为7.48，Q×f约为45800GHz，温度系数约为τf＝-35ppm/℃。
另外，通过适量改变CaMg1-x-yLi2xZnySi2O6，0.1≤x≤0.3中x的值(固定y值为0.15，x的取值范围为0.1～0.3)的值和最终的烧结温度(880℃～920℃)，可以使制备所得材料的微波介电性能(即介电常数、介电损耗和谐振频率温度系数)发生一定的变化，具体如下表所示。表1为固定y为0.15，x变化及烧结温度变化时材料体系的微波介电性能的变化。
表1。
Claims (3)
1.一种无助熔剂的LTCC微波陶瓷材料，其特征在于：
以CaMg1-x-yLi2xZnySi2O6为主晶相，0.1≤x≤0.3，0.1≤y≤0.3，于850℃～950℃烧结，介电常数εr为6.9～7.8，品质因数Q×f值25000GHz～45800GHz，谐振频率温度系数τf为-30～-40ppm/℃；
由原料CaCO3、MgO、Li2CO3、ZnO和SiO2按摩尔比CaCO3：MgO：Li2CO3：ZnO：SiO2＝1:1-x-y:x:y:2配制，通过固相法制得。
该微波陶瓷在作为LTCC微波介质基板或器件材料时，可以显著降低微波器件或模块的损耗。
2.如权利要求1所述无助熔剂的LTCC微波陶瓷材料的制备方法，具体如下：
步骤1、以CaCO3、MgO、Li2CO3、ZnO和SiO2为初始原料，按照CaMg1-x-yLi2xZnySi2O6，0.1≤x≤0.3，0.1≤y≤0.3的陶瓷配方分子式中各元素的摩尔比例折算出CaCO3、MgO、Li2CO3、ZnO和SiO2的质量百分比，进行称料、一次球磨、混料均匀后烘干；
步骤2、将步骤1所得的烘干料过筛后放入坩埚中压实，按1℃～2℃/分的升温速率升至850℃～950℃进行预烧，保温2～3小时，随炉自然冷却得到预烧料；
步骤3、将步骤2所得预烧料在球磨机中进行二次球磨；
步骤4、将步骤3所得到的二次球磨料烘干后，加入质量分数为10％～20％的PVA溶液进行造粒并干压成型；
步骤5、将步骤4所得的样品放入烧结炉中，按1℃～2℃/分的升温速率升至200℃～300℃保温1～2小时后，继续升温至500℃～600℃保温2～4小时，以排除生坯中的水分和胶水；然后再按2℃～5℃/分的升温速率升温至850℃～950℃进行烧结，保温2～3小时，再按2℃～5℃/分的降温速率降温至500℃～600℃，随后随炉自然冷却得到无助熔剂的低介低损耗微波陶瓷材料。
3.如权利要求1所述无助熔剂的LTCC微波陶瓷材料的制备方法，其特征在于：所述PVA溶液的浓度为8～10％。
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