CN112830780B - 一种调控剂、ltcc微波介质材料及其制备方法 - Google Patents

一种调控剂、ltcc微波介质材料及其制备方法 Download PDF

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CN112830780B
CN112830780B CN202110053491.6A CN202110053491A CN112830780B CN 112830780 B CN112830780 B CN 112830780B CN 202110053491 A CN202110053491 A CN 202110053491A CN 112830780 B CN112830780 B CN 112830780B
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李晨辉
程凯
马佳进
邹阳
孙永明
史玉升
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Huazhong University of Science and Technology
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Abstract

本发明属于微波介质材料相关技术领域，其公开了一种调控剂、LTCC微波介质材料及其制备方法，所述调控剂的表达式为Li2Ti0.9Zr0.1Si1‑ mGemO5；所述LTCC微波介质材料包括调控剂、主相(BaxCaySrzMg1‑x‑y‑z)2V2O7或RMoO4以及B物质，其中主相(BaxCaySrzMg1‑x‑y‑z)2V2O7或RMoO4与调控剂的物质的量之比为a：(1‑a)，所述B物质占主相(BaxCaySrzMg1‑x‑y‑z)2V2O7或RMoO4与调控剂的质量之和的b％，0.2≤a≤0.8，0≤x≤1，0≤y≤1，0≤z≤1，0≤m≤1，0≤b≤5。本发明通过调整组分的比例来调节谐振频率温度系数近零，提高Q值，获得超低损耗、低介LTCC微波介质材料，适用于高频通讯及射频领域。

Description

一种调控剂、LTCC微波介质材料及其制备方法
技术领域
本发明属于微波介质材料相关技术领域，更具体地，涉及一种调控剂、 LTCC微波介质材料及其制备方法，进一步地涉及一种低介温频特性调控剂和谐振频率温度系数近零的LTCC微波介质材料及其制备方法。
背景技术
随着5G移动通信技术的发展，一方面，用户对毫米波产品的需求随之增大；另一方面，厂家对设备的小型化、低成本、高可靠性和可批量生产的要求越来越高。用于毫米波通信器件集成技术的关键介质材料——LTCC 微波介质陶瓷材料成为研究热点。服役于毫米波段通信器件的LTCC微波介质材料通常应满足以下三个条件：较低的介电常数(εr)和较高的Q值(即低损耗)以及近零的谐振频率温度系数(τf)。特别地，εr值与电磁信号的交互耦合作用呈正相关，可通过降低介质材料的εr值来提高电磁波的传播速率以实现信号高速传输；τf近零可保证器件热稳定性和可靠性。因此，近年来，低介(εr＜10)、温度稳定型(τf近零)微波介质材料成为5G通讯领域关键基础材料的研究热点之一。
有研究[文献J.Am.Ceram.Soc.92[12]3092-3094(2009)、J.Am.Ceram. Soc.92[7]1621-1624(2009)、Journal of Electronic Materials volume 48[7]972 –976(2019)]指出R2V2O7、RMoO4(R＝Ba,Sr,Ca,Mg)具有低介电常数、低介电损耗、可低温致密化的优点(性能为εr＝6.8-12.11、Q×f＝ 40000～121630GHz、τf＝-84～-26ppm/℃)，在毫米波通信方面具有巨大的应用潜力，但其τf值在负方向较大不利于器件工作的热稳定性和可靠性，难以直接投入生产应用。在工业上，为实现τf值调零，通常采用调控剂(具有正τf值)与基体材料复合的工艺方法，但受微波介质材料的三个性能指标(εr与Q·f和τf)相互制约关系的影响(见文献：微波介质陶瓷材料介电性能间的制约关系，朱建华，梁飞，汪小红，吕文中，电子元件与材料， 2005年3月第3期)，目前市场上大部分的调控剂(正τf值)的介电常数、致密化温度过高。又根据复合法则，这种高介调控剂与主相复合后必定会导致体系的介电常数和致密化温度升高、Q值降低等一系列不良后果，从而无法满足LTCC器件生产及毫米波通信的要求。以商业化材料——硅基橄榄石材料为例，文献报道的橄榄石结构Mg2SiO4具有低介电常数(εr＝6-8)、负τf值(-66ppm/℃)，专利[CN106904960B]中将调控剂Li2TiO3与其复合，虽有效调整τf值近零，但体系的介电常数增加至22，Q值恶化至104GHz。专利[CN 1315134C]中，将调控剂MgTiO3与Mg2SiO4复合导致体系的介电常数增加至28，且致密化温度升高至1300℃。相应地，研究报道将调控剂 Ba3V2O8与主相Ba2V2O7、CaF2掺杂的MgTiO3高介调控剂与CaMoO4复合等同样带来体系介电常数增加、与Ag浆化学匹配失衡的不良影响。在以上案例中，经高介调控剂复合后的不良影响严重阻碍了V-、Mo-基瓷粉的商业化进程。
为此，开发出一类普适的低介、正τf值的温频特性调控剂材料，使其满足复合后既不增加体系的介电常数、又可低温烧结的要求；并基于该低介调控剂，获得性能优良的V-、Mo-基LTCC复合材料是本领域技术人员一直渴望解决但始终难以获得成功的难题。
发明内容
针对现有技术的以上缺陷或改进需求，本发明提供了一种调控剂、 LTCC微波介质材料及其制备方法，本发明通过调增低介调控剂 Li2Ti0.9Zr0.1Si1-mGemO5及主相(BaxCaySrzMg1-x-y-z)2V2O7或RMoO4(R＝Ba,Sr, Ca,Mg)的含量，可将谐振频率温度系数调节到近零，适用于高频通讯及射频领域，得到的微波介质材料具有较低烧结温度、超低损耗、且谐振频率温度系数近零的特点。
为实现上述目的，按照本发明的一个方面，提供了一种调控剂，所述调控剂的介电常数小于10且τf为正值；同时，所述调控剂的表达式为 Li2Ti0.9Zr0.1Si1-mGemO5，0≤m≤1。
本发明还提供了一种调控剂的制备方法，所述制备方法用于制备如上所述的调控剂，其包括以下步骤：按照化学计量比Li2Ti0.9Zr0.1Si1-mGemO5称取原料，将称量好的原料倒入球磨罐中，加入氧化锆球和去离子水，行星球磨4h～12h后取出、烘干、过筛，将过筛后的粉末在700℃～1000℃下煅烧，并保温1h～5h后，冷却至室温，以得到Li2TiSi1-mGemO5粉体，即调控剂。
本发明还提供一种LTCC微波介质材料，所述LTCC微波介质材料的组分包括主相、权利要求1所述的调控剂以及B物质；其中，主相与调控剂的物质的量之比为a：(1-a)，所述B物质占主相与调控剂的质量之和的 b％，0.2≤a≤0.8，0≤x≤1，0≤y≤1，0≤z≤1，0≤b≤5；所述主相的表达式为 (BaxCaySrzMg1-x-y-z)2V2O7或RMoO4。
进一步地，所述B物质为纳米级尺寸的Al2O3、ZnO、CuO、MnO2、 WO3中的至少一种。
进一步地，所述B物质的粒度分布满足D50≤500nm，D90≤800nm。
本发明还提供了一种如上所述的LTCC微波介质材料的制备方法，该制备方法包括以下步骤：提供(BaxCaySrzMg1-x-y-z)2V2O7或RMoO4粉体(R＝ Ba,Sr,Ca,Mg)、Li2Ti0.9Zr0.1Si1- mGemO5粉体及B物质，并进行球磨以得到复合瓷粉，进而以该瓷粉为原料制备得到LTCC微波介质材料；其中， (BaxCaySrzMg1-x-y-z)2V2O7或RMoO4与调控剂Li2Ti0.9Zr0.1Si1-mGemO5的物质的量之比为a：(1-a)，所述B物质占主相(BaxCaySrzMg1-x-y-z)2V2O7或RMoO4与调控剂Li2Ti0.9Zr0.1Si1-mGemO5的质量之和的b％，0.2≤a≤0.8，0≤x≤1，0≤y≤1， 0≤z≤1，0≤m≤1，0≤b≤5。
进一步地，所述制备方法包括如下子步骤：
(1)按照化学计量比(BaxCaySrzMg1-x-y-z)2V2O7称取原料，将称量好的原料倒入球磨罐中，加入氧化锆球和去离子水，球磨4h～12h后取出、烘干、过筛，将过筛后的粉末在1100℃～1250℃下煅烧并保温1h～5h后，冷却至室温，以得到(BaxCaySrzMg1-x-y-z)2V2O7粉体；
(2)按照化学计量比RMoO4称取高纯度MgO、BaCO3、SrCO3、CaCO3、 (NH4)2MoO4或Mo2O3原料，将称量好的原料倒入球磨罐中，加入氧化锆球和去离子水，行星球磨2h～16h后取出、烘干、过150目筛，将过筛后的粉末放到氧化铝坩埚中，在马弗炉中以700℃～850℃煅烧，并保温1h～10h 后，冷却至室温，得到RMoO4粉体；其中R为Ba、Sr、Ca或者Mg；
(3)按照化学计量比Li2Ti0.9Zr0.1Si1-mGemO5称取原料，将称量好的原料倒入球磨罐中，加入氧化锆球和去离子水，行星球磨4h～12h后取出、烘干、过筛，将过筛后的粉末在700℃～1000℃下煅烧，并保温1h～5h后，冷却至室温，以得到Li2Ti0.9Zr0.1Si1-mGemO5粉体，进而将 (BaxCaySrzMg1-x-y-z)2V2O7或RMoO4粉体、Li2Ti0.9Zr0.1Si1-mGemO5粉体及B物质进行球磨以得到LTCC微波介质材料。
进一步地，(BaxCaySrzMg1-x-y-z)2V2O7粉体的原料为纯度大于99.99％的 MgO、BaCO3、SrCO3、CaCO3、NH4VO3或V2O5，D50≤800nm。
进一步地，Li2Ti0.9Zr0.1Si1-mGemO5粉体的原料为纯度大于99.99％的 Li2CO3、TiO2、SiO2、ZrO2及GeO2，D50≤900nm。
进一步地，将所述瓷粉中添加粘接剂后进行造粒并成型成圆柱状块体，再以3℃/min的速度升温至550℃，保温1h以除去粘合剂，然后直接以5℃ /min的速度从550℃升温至800℃～900℃，烧结0.5h～5h小时成瓷，由此得到LTCC微波介质材料。
进一步地，所述粘接剂为聚乙烯醇PVA或聚乙烯醇缩丁醛PVB或羧甲基纤维素钠CMC的水溶液中的至少一种。
总体而言，通过本发明所构思的以上技术方案与现有技术相比，本发明提供的调控剂、LTCC微波介质材料及其制备方法主要具有以下有益效果：
1.本发明通过控制Si/Ge比例形成固溶体，进一步降低εr值和介电损耗，得到一种介电常数低于10、超低损耗、正τf值、纯相的调控剂——Li2Ti0.9Zr0.1Si1-mGemO5材料；当其与低介负τf主相复合时，相较于Ti 基(CaTiO3、TiO2或SrTiO3)等高介调控剂，Li2Ti0.9Zr0.1Si1- mGemO5因具备低介高Q特性不会导致复合体系的介电常数增加和Q值降低。
2.Li2Ti0.9Zr0.1Si1-mGemO5调控剂(0≤m≤1)通过固相法合成，工艺简单，可作为其它低介基体材料的普适调控剂，且复合后不会引起体系的介电常数增加。
3.所选用基体为富低熔点组分(V2O5、Mo2O3)的碱土金属盐，低熔点的V2O5或Mo2O3可分别在690℃、795℃时形成液相以利于颗粒流动从而促进烧结，无需添加玻璃助剂可使体系形成低温烧结(致密化温度降低至900℃以下)，可保证体系具有超低介电损耗。
4.通过添加纳米级物质B改善烧结特性，可进一步降低介电损耗，得到一种超低介电常数，超低损耗且τf近零的LTCC介质陶瓷。
5.本发明所述微波介质材料通过―低介调控剂+主相+B物质”设计，可获得无玻璃化材料的介电常数低为7.9～9.9，品质因数高为30000～ 155000GHz，谐振频率温度系数为-40～+35ppm/℃，谐振频率温度系数连续可调，适用于毫米波通讯及射频领域。
附图说明
图1是本发明提供的LTCC微波介质材料的组成示意图；
图2是本发明提供的LTCC微波介质材料的XRD图；
图3是本发明提供的低介调控剂偏离给定合成条件的XRD图；
图4中的(a)～(d)本发明制备的LTCC微波介质陶瓷的示意图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，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仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
请参阅图1，本发明提供的低介温频调控剂为介电常数低于10且同时具备正τf值、超低损耗的单相材料(参阅图2)，具有普适调控效果；本发明提供的LTCC微波介质材料的制备无需添加玻璃相，直接改变低介调控剂和主相的相对含量来获得低介、超低损耗、低温、τf近零的复合效果。
其中，LTCC微波介质材料的主相为：富低熔点金属氧化物(V2O5、 Mo2O3)组分、高Q值(tanδ<10-4)、负τf值的材料；温频特性调控剂与主相化学兼容、共烧匹配。
结合满足上述要求的主相材料，利用所得的调控剂，可以得到一类 LTCC材料。所述LTCC微波介质材料的组分包括主相 (BaxCaySrzMg1-x-y-z)2V2O7或RMoO4、调控剂Li2Ti0.9Zr0.1Si1-mGemO5以及B物质，其中，主相(BaxCaySrzMg1-x-y-z)2V2O7或RMoO4与调控剂Li2Ti0.9Zr0.1Si1-mGemO5的物质的量之比为a：(1-a)，所述B物质占主相 (BaxCaySrzMg1-x-y-z)2V2O7或RMoO4与调控剂Li2Ti0.9Zr0.1Si1-mGemO5的质量之和的b％，0.2≤a≤0.8，0≤x≤1，0≤y≤1，0≤z≤1，0≤m≤1，0≤b≤5，优选地，0≤b≤2。若B物质的加入量超过5wt％，将生成新的化合物，得到的微波介质陶瓷的各项性能将偏离实验值；若Li2Ti0.9Zr0.1Si1-mGemO5的粒度分布范围、预烧温度、球磨时间超过或低于给定条件，将生成第二相，无法得到纯相调控剂(参见图3)。本实施方式中，所述B物质为纳米级尺寸的Al2O3、ZnO、 CuO、MnO2、WO3中的至少一种。
按照本发明的一方面，本发明提供的如上所述的一种LTCC微波介质材料的制备方法包括以下步骤：提供(BaxCaySrzMg1-x-y-z)2V2O7粉体、Li2Ti0.9Zr0.1Si1-mGemO5粉体及B物质，并进行球磨以得到瓷粉，进而以该瓷粉为原料制备得到LTCC微波介质材料；其中，(BaxCaySrzMg1-x-y-z)2V2O7与调控剂Li2Ti0.9Zr0.1Si1-mGemO5的物质的量之比为a：(1-a)，所述B物质占主相(BaxCaySrzMg1-x-y-z)2V2O7与调控剂Li2Ti0.9Zr0.1Si1-mGemO5的质量之和的b％，0.2≤a≤0.8，0≤x≤1，0≤y≤1，0≤z≤1，0≤m≤1，0≤b≤5。
具体地，包括以下子步骤：
(1)按照化学计量比(BaxCaySrzMg1-x-y-z)2V2O7称取高纯度MgO、BaCO3、 SrCO3、CaCO3及NH4VO3或(V2O5)原料(其中0≤x≤1，0≤y≤1，0≤z≤1)，将称量好的原料倒入球磨罐中，加入氧化锆球和去离子水，行星球磨4～12h，取出、烘干、过150目筛，将过筛后的粉末放到氧化铝坩埚中，在马弗炉中以600～850℃煅烧，保温1～5h，冷却至室温，得到(BaxCaySrzMg1-x-y-z)2V2O7粉体；其他方法制备的(BaxCaySrzMg1-x-y-z)2V2O7粉体也可用于此微波介质陶瓷的制备。
(2)按照化学计量比Li2Ti0.9Zr0.1Si1-mGemO5(其中0≤m≤1)称取Li2CO3、 TiO2、ZrO2、SiO2及GeO2原料，将称量好的原料倒入球磨罐中，加入氧化锆球和去离子水，行星球磨4-12h，取出、烘干、过150目筛，获得粒度分布为D50≤600nm粉末，将所得粉末的放到氧化铝坩埚中，在马弗炉中以 700～1100℃煅烧，保温1～5h，冷却至室温，得到Li2Ti0.9Zr0.1Si1- mGemO5粉体；其他方法制备的Li2Ti0.9Zr0.1Si1-mGemO5粉体也可用于此微波介质陶瓷的制备。
(3)按照a BaxCaySrzMg1-x-y-z)2V2O7+(1-a)Li2Ti0.9Zr0.1Si1-mGemO5+b wt％ B物质的比例称取上述所(MgxCaySrzBa1-x-y-z)2V2O7、Li2Ti0.9Zr0.1Si1-mGemO5及B物质粉体，其中0.2≤a≤0.8，b为B物质占BaxCaySrzMg1-x-y-z)2V2O7及 Li2Ti0.9Zr0.1Si1-mGemO5总重量的质量百分比，其中B物质为高纯度经预处理粉碎所得的纳米级Al2O3、ZnO、CuO、V2O5、WO3(纯度≥99.9％)中的至少一种，0≤b≤5，将称量好的粉体倒入球磨罐中，加入氧化锆球和去离子水，行星球磨2～6h，取出、烘干、打粉，得到用于制备LTCC微波介质陶瓷的瓷粉。
(4)在得到的瓷粉中添加5～15wt％的聚乙烯醇PVA(或聚乙烯醇缩丁醛PVB或羧甲基纤维素钠CMC中的至少一种)水溶液、造粒并成型成圆柱状块体(所述成型方式可为干压成型、冷等静压成型、热等静压成型等)，以3℃/min的速度升温至550℃，保温1h以除去粘合剂，然后直接以5℃/min 的速度从550℃升温至800～900℃烧结0.5～5h小时成瓷，随炉冷却后从坩埚内取出样品，得到LTCC微波介质陶瓷(参见图4中的(a)-(b))。
所得样品的直径和厚度使用千分尺测量，借助AgilentE8363A PNA网络分析仪，采用空腔法测量所制备圆柱形陶瓷材料的介电常数和介电损耗，将测试样品放入ESPEC高低温循环箱进行谐振频率温度系数的测量，温度范围为20℃～100℃，测试频率在6GHz～16GHz范围内。
以下以具体实施例来对本发明进行进一步地详细说明。
对比例1
按上述制备方法，选定a＝0，b＝0的情况，用网络分析仪和谐振腔测试步骤(1-4)制得的Li2Ti0.9Zr0.1Si1-mGemO5微波介质陶瓷的微波介电性能。测试结果详见表1。所得瓷粉的XRD结果图见图2。
表1为对比例1中设计的实验结果
Figure BDA0002900026150000081
对比例2
若偏离上述制备方法给定条件，如改变球磨时间、烧结温度、粒度分布，制备名义组成为Li2Ti0.9Zr0.1Si1-mGemO5的材料将出现第二相，所得瓷粉的XRD结果图见图3，微波介电性能测试结果详见表2。
表2为对比例2中设计的实验结果
Figure BDA0002900026150000091
从对比例1和2中可以看出，通过调整Si/Ge含量可以得到一种低介、超低损耗、正τf值、纯相的调控剂——Li2Ti0.9Zr0.1Si1-mGemO5材料。若偏离给定条件，所得材料各项性能将不符合设计要求。
实施例1
按上述制备方法，在对比例1的基础上，选取m＝0.6(对比例1#编号3)，控制b＝0，调整x、y、z、a的值。具体实施例的相关工艺参数和微波介电性能的测试结果详见表3。
表3具体实施例及对应样品的微波介电性能
Figure BDA0002900026150000092
实施例2
仿照实施例1，在实施例1的基础上选取x＝0，y＝0，z＝1，a＝0.6， m＝0.6组分(实施例1#编号6)，在第(3)步中添加B物质含量为1wt％(即b ＝1)，其余步骤与实施例1相同，测试结果详见表4。
表4具体实施例及对应样品的微波介电性能
Figure BDA0002900026150000101
实施例3
仿照实施例2，在实施例2的基础上，选取B物质为ZnO(实施例2# 编号2)，改变B物质的添加量，其余步骤与实施例2相同，测试结果详见表5。
表5具体实施例及对应样品的微波介电性能
Figure BDA0002900026150000102
从实施例1-3中可以看出，利用给定的Li2Ti0.9Zr0.1Si1-mGemO5调控剂，通过调整BaxCaySrzMg1-x-y-z)2V2O7、Li2Ti0.9Zr0.1Si1-mGemO5及B物质的比例，提高Q值，可以调节谐振频率温度系数近零，获得超低损耗、低介LTCC 微波介质材料。
所得样品的直径和厚度使用千分尺测量，借助AgilentE8363A PNA网络分析仪，采用空腔法测量所制备圆柱形陶瓷材料的介电常数和介电损耗，将测试样品放入ESPEC高低温循环箱进行谐振频率温度系数的测量，温度范围为20℃～100℃，测试频率在6GHz～16GHz范围内。
利用该低介调控剂的调控效果，本发明提供一种LTCC微波介质材料的制备方法包括以下步骤：提供RMoO4(R＝Ba，Sr，Ca，Mg)粉体、 Li2Ti0.9Zr0.1Si1-mGemO5粉体及B物质，并进行球磨以得到瓷粉，进而以该瓷粉为原料制备得到LTCC微波介质材料；其中，主相RMoO4与调控剂 Li2Ti0.9Zr0.1Si1-mGemO5的物质的量之比为a：(1-a)，所述B物质占主相主相 RMoO4与调控剂Li2Ti0.9Zr0.1Si1-mGemO5的质量之和的b％，0.2≤a≤0.8，0≤m≤1， 0≤b≤5。
具体地，包括以下子步骤：
(1)按照化学计量比RMoO4(R＝Ba，Sr，Ca，Mg)称取高纯度MgO、 BaCO3、SrCO3、CaCO3、(NH4)2MoO4或Mo2O3原料，将称量好的原料倒入球磨罐中，加入氧化锆球和去离子水，行星球磨2～16h后取出、烘干、过 150目筛，将过筛后的粉末放到氧化铝坩埚中，在马弗炉中以700～850℃煅烧，保温1～10h后冷却至室温，得到RMoO4(R＝Ba，Sr，Ca，Mg)粉体；其他方法制备的RMoO4(R＝Ba，Sr，Ca，Mg)粉体也可用于此微波介质陶瓷的制备。
(2)按照化学计量比Li2Ti0.9Zr0.1Si1-mGemO5(其中0≤m≤1)称取Li2CO3、 TiO2、ZrO2、SiO2及GeO2原料，将称量好的原料倒入球磨罐中，加入氧化锆球和去离子水，行星球磨4-12h后取出、烘干、过150目筛，将过筛后的粉末放到氧化铝坩埚中，在马弗炉中以700～1000℃煅烧，保温1～5h，冷却至室温，得到Li2Ti0.9Zr0.1Si1-mGemO5粉体；其他方法制备的Li2Ti0.9Zr0.1Si1-mGemO5粉体也可用于此微波介质陶瓷的制备。
(3)按照a RMoO4(R＝Ba，Sr，Ca，Mg)+(1-a)Li2Ti0.9Zr0.1Si1-mGemO5 +b wt％B物质的比例称取上述所RMoO4(R＝Ba，Sr，Ca，Mg)、 Li2Ti0.9Zr0.1Si1-mGemO5及B物质粉体，其中0.2≤a≤0.8，b为B物质占RMoO4 (R＝Ba，Sr，Ca，Mg)及Li2Ti0.9Zr0.1Si1-mGemO5总重量的质量百分比，其中B物质为高纯度经预处理粉碎所得的纳米级Al2O3、ZnO、CuO、V2O5、 WO3(纯度≥99.9％)中的至少一种，0≤b≤5，将称量好的粉体倒入球磨罐中，加入氧化锆球和去离子水，行星球磨2～6h，取出、烘干、打粉，得到用于制备LTCC微波介质陶瓷的瓷粉。
(4)在得到的瓷粉中添加5～15wt％的聚乙烯醇PVA(或聚乙烯醇缩丁醛PVB或羧甲基纤维素钠CMC中的至少一种)水溶液、造粒并成型成圆柱状块体(所述成型方式可为干压成型、冷等静压成型、热等静压成型等)，以3℃/min的速度升温至550℃，保温1h以除去粘合剂，然后直接以5℃/min 的速度从550℃升温至700～900℃烧结0.5～10h小时成瓷，随炉冷却后从坩埚内取出样品，得到LTCC微波介质陶瓷(参见图4中的(c)-(d))。
以下以具体实施例来对本发明进行进一步地详细说明。
实施例4
按上述制备方法，在对比例1的基础上，调整a、b、m的值。具体实施例的相关工艺参数和微波介电性能的测试结果详见表6。
表6具体实施例及对应样品的微波介电性能
Figure BDA0002900026150000121
从实施例4中可以看出，Li2Ti0.9Zr0.1Si1-mGemO5材料调控剂，通过调整 RMoO4(R＝Ba，Sr，Ca，Mg)、Li2Ti0.9Zr0.1Si1-mGemO5及B物质的比例，提高Q值，可以调节谐振频率温度系数近零，获得超低损耗、低介LTCC 微波介质材料。进一步表明该调控剂的调控效果。
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

1.一种调控剂，其特征在于：所述调控剂的介电常数小于10且τf为正值；同时，所述调控剂的表达式为Li2Ti0.9Zr0.1Si1-mGemO5，0<m<1。
2.一种调控剂的制备方法，其特征在于：所述制备方法用于制备权利要求1所述的调控剂，其包括以下步骤：按照化学计量比Li2Ti0.9Zr0.1Si1-mGemO5称取原料，将称量好的原料倒入球磨罐中，加入氧化锆球和去离子水，行星球磨4h～12h后取出、烘干、过筛，将过筛后的粉末在700℃～1000℃下煅烧，并保温1h～5h后，冷却至室温，以得到Li2TiSi1-mGemO5粉体，即调控剂。
3.一种LTCC微波介质材料，其特征在于：所述LTCC微波介质材料的组分包括主相、权利要求1所述的调控剂以及B物质；其中，主相与调控剂的物质的量之比为a：(1-a)，所述B物质占主相与调控剂的质量之和的b％，0.2≤a≤0.8，0≤x≤1，0≤y≤1，0≤z≤1，0≤b≤5；所述主相的表达式为(BaxCaySrzMg1-x-y-z)2V2O7或RMoO4，其中R＝Ba，Sr，Ca，Mg。
4.如权利要求3所述的LTCC微波介质材料，其特征在于：所述B物质为纳米级尺寸的Al2O3、ZnO、CuO、MnO2、WO3中的至少一种。
5.一种权利要求3-4任一项所述的LTCC微波介质材料的制备方法，其特征在于，该制备方法包括以下步骤：提供(BaxCaySrzMg1-x-y-z)2V2O7或RMoO4粉体、Li2Ti0.9Zr0.1Si1-mGemO5粉体及B物质，并进行球磨以得到复合瓷粉，进而以该瓷粉为原料制备得到LTCC微波介质材料；其中，(BaxCaySrzMg1-x-y-z)2V2O7或RMoO4与调控剂Li2Ti0.9Zr0.1Si1-mGemO5的物质的量之比为a：(1-a)，所述B物质占主相(BaxCaySrzMg1-x-y-z)2V2O7或RMoO4与调控剂Li2Ti0.9Zr0.1Si1-mGemO5的质量之和的b％，0.2≤a≤0.8，0≤x≤1，0≤y≤1，0≤z≤1，0≤m≤1，0≤b≤5。
6.如权利要求5所述的LTCC微波介质材料的制备方法，其特征在于：所述制备方法包括如下子步骤：
(1)按照化学计量比(BaxCaySrzMg1-x-y-z)2V2O7称取原料，将称量好的原料倒入球磨罐中，加入氧化锆球和去离子水，球磨4h～12h后取出、烘干、过筛，将过筛后的粉末在1100℃～1250℃下煅烧并保温1h～5h后，冷却至室温，以得到(BaxCaySrzMg1-x-y-z)2V2O7粉体；
(2)按照化学计量比RMoO4称取高纯度MgO、BaCO3、SrCO3、CaCO3、(NH4)2MoO4或Mo2O3原料，将称量好的原料倒入球磨罐中，加入氧化锆球和去离子水，行星球磨2h～16h后取出、烘干、过150目筛，将过筛后的粉末放到氧化铝坩埚中，在马弗炉中以700℃～850℃煅烧，并保温1h～10h后，冷却至室温，得到RMoO4粉体；其中R为Ba、Sr、Ca或者Mg；
(3)按照化学计量比Li2Ti0.9Zr0.1Si1-mGemO5称取原料，将称量好的原料倒入球磨罐中，加入氧化锆球和去离子水，行星球磨4h～12h后取出、烘干、过筛，将过筛后的粉末在700℃～1000℃下煅烧，并保温1h～5h后，冷却至室温，以得到Li2Ti0.9Zr0.1Si1-mGemO5粉体，进而将(BaxCaySrzMg1-x-y-z)2V2O7或RMoO4粉体、Li2Ti0.9Zr0.1Si1-mGemO5粉体及B物质进行球磨以得到LTCC微波介质材料。
7.如权利要求6所述的LTCC微波介质材料的制备方法，其特征在于：(BaxCaySrzMg1-x-y-z)2V2O7粉体的原料为纯度大于99.99％的MgO、BaCO3、SrCO3、CaCO3、NH4VO3或V2O5，D50≤800nm。
8.如权利要求6所述的LTCC微波介质材料的制备方法，其特征在于：Li2Ti0.9Zr0.1Si1- mGemO5粉体的原料为纯度大于99.99％的Li2CO3、TiO2、SiO2、ZrO2及GeO2，D50≤900nm。
9.如权利要求6所述的LTCC微波介质材料的制备方法，其特征在于：将所述瓷粉中添加粘接剂后进行造粒并成型成圆柱状块体，再以3℃/min的速度升温至550℃，保温1h以除去粘合剂，然后直接以5℃/min的速度从550℃升温至800℃～900℃，烧结0.5h～5h成瓷，由此得到LTCC微波介质材料。
10.如权利要求9所述的LTCC微波介质材料的制备方法，其特征在于：所述粘接剂为聚乙烯醇PVA或聚乙烯醇缩丁醛PVB或羧甲基纤维素钠CMC的水溶液中的至少一种。
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