CN114835987B - 一种微米级表面多孔型SiO2基微波复合介质基板及其制备方法 - Google Patents
一种微米级表面多孔型SiO2基微波复合介质基板及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种微米级表面多孔型SiO2基微波复合介质基板及其制备方法。用于高频高速环境的具有低介电常数、低介电损耗、低热膨胀系数的微波复合介质基板的制备，其困难点之一在于填料与基体界面结合不佳。本发明通过刻蚀构筑了微米级表面多孔型二氧化硅球，将表面多孔的微米级二氧化硅球与聚四氟乙烯混合，通过压延成型和真空热压法使表面多孔的微米级二氧化硅球与聚合物基体混合均匀，使板材致密，表面多孔的微米级二氧化硅填料的加入，使微波复合介质基板不仅保持较低介电常数，且多孔层与聚四氟乙烯的良好界面结合使得微波复合介质基板兼具较低的介电损耗及热膨胀系数。本发明制备方法条件简单、成本较低、产率较高，适用于基板批量生产。
Description
技术领域
本发明涉及微波介电领域，具体地指一种微米级表面多孔型SiO2基微波复合介质基板及其制备方法，可应用于5G高频电路板的制造。
背景技术
随着互联网5G的逐渐普及，人们对信息处理和通信的需求与日俱增。对功能信息材料的发展逐渐向着设备的小型化、高集成度和高频方向发展。根据应用环境需求，高频高速基板材料需要具有优异的介电性能，即低介电常数和低介电损耗。同时，为避免工作环境下温度过高引起的尺寸变化和热失效作用，高频高速基板材料需要较低的热膨胀系数。
PTFE因其具有较低的介电常数和介电损耗，以及频率温度稳定性高等优势，使其被认为是高频介质板中最重要的材料，但其较高的热膨胀系数严重限制了它的实际应用场景。
针对PTFE树脂存在的热膨胀系数较高的缺点，可通过添加一定量的SiO2填料改善，由于SiO2的介电常数较低，因而，可以在降低PTFE热膨胀系数的同时保持较低的介电常数。然而，目前SiO2与PTFE树脂混合制备复合介质基板还存在以下问题：
(1)易原位合成的表面多孔型SiO2纳米球，其表面多孔层可与PTFE树脂形成良好的界面结合，但由于纳米级SiO2表面能过大，使得其自身极易团聚，难以完全分散，从而易使得制备的复合基质基板性能不稳定；
(2)文献Synthesis of Monodisperse Silica Microspheres by a ModifiedStober Method中公开了微米级实心二氧化硅球的制备方法，微米级SiO2由于颗粒尺寸较大，虽然相对于纳米级SiO2而言更不易自身团聚，但在合成过程中，难以控制其表面多孔结构的形成，而表面光滑的微米级SiO2与PTFE界面结合不好，从而使得其介电损耗增大。
发明内容
本发明的目的就是要解决上述背景技术的不足，提供一种步骤简单、成本低廉、兼具较低介电损耗及热膨胀系数的微米级表面多孔型SiO2基微波复合介质基板及其制备方法。
本发明的技术方案为：一种微米级表面多孔型SiO2基微波复合介质基板的制备方法，其特征在于，包括以下步骤：
(1)将浓硝酸、氢氟酸、去离子水混合得到刻蚀溶液，将微米级实心二氧化硅球分散于刻蚀溶液中，在10～50℃水浴条件下进行刻蚀，刻蚀完毕经洗涤、烘干、研磨、煅烧处理，得到微米级表面多孔型二氧化硅；
(2)将微米级表面多孔型二氧化硅与聚四氟乙烯乳液混合，得到有机-无机共混物；
(3)将所述有机-无机共混物采用压延混炼工艺压延成型，得到复合材料预压片；
(4)将所述复合材料预压片真空热压烧结，得到微波复合介质基板。
优选的，步骤(1)中浓硝酸、氢氟酸、去离子水按体积比1:(0.25～0.75):(5～8)混合得到刻蚀溶液。本发明中，浓硝酸、氢氟酸、去离子水的体积比十分关键，这是由于只有在适宜的体积比时，才能在微米级实心二氧化硅表面构筑出所需的多孔结构，浓硝酸体积过量会造成微米级实心二氧化硅表面不稳定，使得刻蚀难以形成其表面多孔结构；体积过少会造成微米级实心二氧化硅表面过于稳定，难以产生刻蚀效果；氢氟酸体积过量会造成微米级实心二氧化硅直接溶解，体积过少会造成刻蚀形成的多孔结构达不到所需的形貌。
优选的，步骤(1)中使用的微米级实心二氧化硅球的平均粒径D50为1.2～5.5μm。
优选的，步骤(1)中刻蚀时间为1～10h。本发明中，刻蚀时间十分重要，时间过长会造成微米级实心二氧化硅表面多孔结构消失，过短会造成刻蚀溶液与微米级实心二氧化硅表面还未发生刻蚀反应，即被洗涤烘干，从而难以达到刻蚀效果。刻蚀需在10～50℃水浴条件下完成，这是由于温度过低，刻蚀速率过慢，这会使获得微米级实心二氧化硅表面多孔结构的时间过长；温度过高，刻蚀速率过快，这会使得难以控制刻蚀溶液在微米级实心二氧化硅表面的刻蚀效果，更优选为20～40℃，这是由于在这个温范围内，刻蚀速率是适宜的，方便控制刻蚀溶液在微米级实心二氧化硅表面的刻蚀效果。
优选的，步骤(1)中烘干为60～100℃下5～10h，煅烧为550～750℃下3～8h。
优选的，步骤(2)中聚四氟乙烯乳液固含量40～70wt％，有机-无机共混物中微米级表面多孔型二氧化硅的含量为10～50wt％。
优选的，步骤(2)混合时间为1～4min。
优选的，步骤(3)中压延成型为采用三辊压延机多次压延，所述复合材料预压片的厚度为1.0～1.5mm。本发明采用压延混炼的方式，均匀性好，可操作性强，可实现体系中PTFE树脂、微米级表面多孔型二氧化硅均匀混合。
优选的，步骤(4)中真空热压的压强为40～60MPa，热压时间4～8h，热压温度为360～400℃。
本发明还提供一种上述方法制得的用于高频高速环境下的微米级表面多孔型SiO2基微波复合介质基板。
优选的，所述微波复合介质基板的介电常数为2.1～2.5，介电损耗为1.6×10-3～2.4×10-3，热膨胀系数为46～56ppm/℃。
本发明采用微米级实心二氧化硅与PTFE乳液，微米级实心二氧化硅相对纳米级实心二氧化硅而言，不易团聚，在PTFE中易分散均匀；使其不仅保持了较低的介电常数，且多孔层与PTFE的良好界面结合使得复合材料兼具了较低的介电损耗及热膨胀系数，是一种十分具有潜力的低介复合介质基板材料。基板通过二氧化硅表面多孔的结构构筑，由于多孔层与PTFE良好的界面结合，使得降低了基板的介电损耗，同时达到降低其热膨胀系数的目的。
本发明的有益效果：
(1)本发明采用微米级实心二氧化硅球为原料，通过刻蚀构筑了表面多孔结构的微米级实心二氧化硅球。采用上述微米级表面多孔二氧化硅球与PTFE混合，所制得的微波复合介质基板不仅保持了较低的介电常数，且多孔层与PTFE的良好界面结合使得微波复合介质基板兼具了较低的介电损耗及热膨胀系数；
(2)本发明采用的微米级表面多孔型低介电二氧化硅球，其颗粒尺寸相对纳米级二氧化硅球而言更大，因而其表面能更低，使其自身不易团聚，从而其能与PTFE混合的更加均匀，实现本体系中PTFE树脂、微米级表面多孔型二氧化硅球均匀混合。
附图说明
图1是对照组中的微米级实心二氧化硅粉体SEM图；
图2是实施例1中刻蚀后的微米级实心二氧化硅SEM图；
图3是对照组中微米级实心二氧化硅的颗粒粒径图；
图4是实施例1中刻蚀后的微米级实心二氧化硅的颗粒粒径图；
图5是对照组中微波复合介质基板断面SEM图；
图6是实施例1中微波复合介质基板断面SEM图；
图7为对照组与实施例1～3中微波复合介质基板介电常数图；
图8为对照组与实施例1～3中微波复合介质基板介电损耗图。
具体实施方式
下文将结合具体实施例对本发明的技术方案做更进一步的详细说明。下列实施例仅为示例性地说明和解释本发明，而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。
除非另有说明，以下实施例中使用的原料和试剂均为市售商品，或者可以通过已知方法制备(微米级实心二氧化硅球为按文献Synthesis of Monodisperse SilicaMicrospheres by a Modified Stober Method公开方法制备得到)。
对照组
本实施例提供一种微米级实心SiO2基微波复合介质基板的制备方法，步骤如下：
(1)将微米级实心二氧化硅球(D50粒径为1.2μm)加入到固含量为60wt％的PTFE树脂中，用混料机充分搅拌至混合均匀，混合时间为2min，得到微米级实心二氧化硅含量为30wt％的有机-无机共混物；
(2)将上述有机-无机共混物采用压延混炼的方式成型，使用三辊压延机经过两次压延得到一定厚度1.0μm的复合材料预压片；
(3)将上述复合材料预压片采用叠层的方式进行真空热压烧结处理，其中，叠层是将几片复合材料预压片叠好后上下两面分别加上两层铜箔，叠好的基片板材放置于两块钢板之间，置于热压机中，先抽真空随后进行热压烧结，冷却至室温后得到微波复合介质基板，所述真空热压的压强为50MPa，时间为8h，温度为385℃。
实施例1
本实施例提供一种微米级表面多孔型SiO2基微波复合介质基板的制备方法，步骤如下：
(2)采用浓硝酸(市售质量分数65％～68％浓硝酸产品)、氢氟酸(市售质量分数≥40％氢氟酸的产品)及去离子水按体积比为1:0.75:7的比例配制刻蚀溶液，以微米级实心二氧化硅球(平均粒径D50粒径为1.2μm)为原料加入刻蚀溶液中，在35℃水浴条件下刻蚀5h，通过刻蚀构筑了表面多孔结构的二氧化硅球。刻蚀完毕后将固体用去离子水洗涤、离心数次，80℃烘6h后研磨得到白色粉末；
(3)将上述白色粉末置于坩埚中，用马弗炉进行煅烧处理去除二氧化硅中的有机物，高温处理的反应温度为700℃，时间为4h，即可得到微米级表面多孔二氧化硅球，平均粒径D50为1.2μm，微观结构如图2所示；
(4)将上述微米级表面多孔二氧化硅球加入到固含量为60wt％的PTFE树脂中，用双中心混料机搅拌2min混合均匀，得到微米级表面多孔型二氧化硅含量为30wt％的有机-无机共混物；
(5)将上述有机-无机共混物采用混炼压延的方式成型，使用三辊压延机经过两次压延得到厚度1.0mm的复合材料预压片；
(6)将上述复合材料预压片采用叠层的方式进行真空热压烧结处理，其中，叠层是将几片复合材料预压片叠好后上下两面分别加上两层铜箔，叠好的基片板材放置于两块钢板之间，置于热压机中，先抽真空随后进行热压烧结，冷却至室温后得到微波复合介质基板，所述真空热压的压强为50MPa，时间为8h，温度为385℃。
实施例2
本实施例提供一种微米级表面多孔型SiO2基微波复合介质基板的制备方法，步骤如下：
(1)采用浓硝酸(市售质量分数65％～68％浓硝酸产品)、氢氟酸(市售质量分数≥40％氢氟酸产品)及去离子水按体积比为1:0.5:5的比例配制刻蚀溶液，以上述方法制备的微米级实心二氧化硅球(平均粒径D50为2.2μm)为原料加入刻蚀溶液中，在10℃水浴条件下刻蚀10h，通过刻蚀构筑了表面多孔结构的二氧化硅球。刻蚀完毕后将固体用去离子水洗涤、离心数次，60℃烘10h后研磨得到白色粉末；
(3)将上述白色粉末置于坩埚中，用马弗炉进行煅烧处理去除二氧化硅中的有机物，高温处理的反应温度为650℃，时间为5h，即可得到微米级表面多孔二氧化硅球，平均粒径D50为2.2μm；
(4)将上述微米级表面多孔二氧化硅球加入到固含量为40wt％的PTFE树脂中，用双中心混料机搅拌1min混合均匀，得到微米级表面多孔型二氧化硅含量为10wt％的有机-无机共混物；
(5)将上述有机-无机共混物采用混炼压延的方式成型，使用三辊压延机经过两次压延得到厚度1.2mm的复合材料预压片；
(6)将上述复合材料预压片采用叠层的方式进行真空热压烧结处理，其中，叠层是将几片复合材料预压片叠好后上下两面分别加上两层铜箔，叠好的基片板材放置于两块钢板之间，置于热压机中，先抽真空随后进行热压烧结，冷却至室温后得到微波复合介质基板，所述真空热压的压强为40MPa，时间为4h，温度为400℃。
实施例3
本实施例提供一种微米级表面多孔型SiO2基微波复合介质基板的制备方法，步骤如下：
(1)采用浓硝酸(市售质量分数65％～68％浓硝酸产品)、氢氟酸(市售质量分数≥40％氢氟酸产品)及去离子水按体积比为1:0.25:8的比例配制刻蚀溶液，以微米级实心二氧化硅球(D50粒径为5.5μm)为原料加入刻蚀溶液中，在50℃水浴条件下刻蚀1h，通过刻蚀构筑了表面多孔结构的二氧化硅球。刻蚀完毕后将固体用去离子水洗涤、离心数次，100℃烘5h后研磨得到白色粉末；
(3)将上述白色粉末置于坩埚中，用马弗炉进行煅烧处理去除二氧化硅中的有机物，高温处理的反应温度为750℃，时间为3h，即可得到微米级表面多孔二氧化硅球，平均粒径D50为5.5μm；
(4)将上述微米级表面多孔二氧化硅球加入到固含量为70wt％的PTFE树脂中，用双中心混料机搅拌4min混合均匀，得到微米级表面多孔型二氧化硅含量为50wt％的有机-无机共混物；
(5)将上述有机-无机共混物采用混炼压延的方式成型，使用三辊压延机经过两次压延得到厚度1.5mm的复合材料预压片；
(6)将上述复合材料预压片采用叠层的方式进行真空热压烧结处理，其中，叠层是将几片复合材料预压片叠好后上下两面分别加上两层铜箔，叠好的基片板材放置于两块钢板之间，置于热压机中，先抽真空随后进行热压烧结，冷却至室温后得到微波复合介质基板，所述真空热压的压强为60MPa，时间为6h，温度为360℃。
性能测试
(一)扫描电镜测试
将微米级二氧化硅球刻蚀前后进行扫描电镜分析，分别得到图1、图2；
对比图1、图2可知，刻蚀后的微米级实心二氧化硅球表面呈多孔结构；而刻蚀前的微米级实心二氧化硅球表面则是光滑的，无多孔结构。
将对照组、实施例1所制得的微波复合介质基板的断面进行扫描电镜分析，分别得到图5、图6。
对比图5、图6可知，图5中二氧化硅与PTFE之间的结合，明显存在较宽的缝隙，界面结合不佳；实施例1中多孔二氧化硅球与PTFE之间的结合缝隙更少，界面结合更好。
(二)颗粒粒径测试
将实施例1微米级实心二氧化硅球刻蚀前后进行颗粒粒径测试分析，分别得到图3、图4；
对比图3、图4可知，刻蚀前后的微米级实心二氧化硅球颗粒粒径分布范围基本一致，D50均为1.2μm左右。
(二)介电常数、介电损耗及热膨胀系数测试
将对照组、实施例1～3所制得的微波复合介质基板在测试频率为30GHz下分别进行介电常数、介电损耗测试，以及测试了该复合介质基板的热膨胀系数，得到下表数据：
由上表可知，本发明所述微波复合介质基板具有低介电常数、低介电损耗、低热膨胀系数的特点，介电常数在2.1～2.5范围内，介电损耗在1.6×10-3～2.4×10-3范围内，热膨胀系数在46～56ppm/℃范围内。
对照组与实施例1～3中微波复合介质基板介电常数如图7所示，相对于未刻蚀的二氧化硅而言，刻蚀后的二氧化硅(实施例1–2)与PTFE制备的微波复合介质基板介电常数更低；对于实施例3(当刻蚀后的二氧化硅填料加到50wt％时)，在其热膨胀系数(仅为46ppm/℃)明显低于对比例(58ppm/℃)的情况下，其介电常数也是与对照组相近。
对照组与实施例1～3中微波复合介质基板介电损耗如图8所示，相对于未刻蚀的二氧化硅而言，刻蚀后的二氧化硅与PTFE制备的微波复合介质基板介电损耗更低。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，但本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (6)
1.一种微米级表面多孔型SiO2基微波复合介质基板的制备方法，其特征在于，包括以下步骤：
(1)将浓硝酸、氢氟酸、去离子水按体积比1:(0.25～0.75):(5～8)混合得到刻蚀溶液，将微米级实心二氧化硅球分散于刻蚀溶液中，微米级实心二氧化硅球的平均粒径D50为1.2～5.5μm，在10～50℃水浴条件下进行刻蚀，刻蚀时间为1～10h，刻蚀完毕经洗涤、烘干、研磨、煅烧处理，得到微米级表面多孔型二氧化硅；
(2)将微米级表面多孔型二氧化硅与聚四氟乙烯乳液混合，得到有机-无机共混物，聚四氟乙烯乳液固含量40～70wt％，有机-无机共混物中微米级表面多孔型二氧化硅的含量为10～50wt％；
(3)将所述有机-无机共混物采用压延混炼工艺压延成型，得到复合材料预压片；
(4)将所述复合材料预压片真空热压烧结，得到微波复合介质基板。
2.如权利要求1所述的微米级表面多孔型SiO2基微波复合介质基板的制备方法，其特征在于，步骤(1)中烘干为60～100℃下5～10h，煅烧为550～750℃下3～8h。
3.如权利要求1所述的微米级表面多孔型SiO2基微波复合介质基板的制备方法，其特征在于，步骤(2)混合时间为1～4min。
4.如权利要求1所述的微米级表面多孔型SiO2基微波复合介质基板的制备方法，其特征在于，步骤(4)中真空热压的压强为40～60MPa，热压时间4～8h，热压温度为360～400℃。
5.一种微米级表面多孔型SiO2基微波复合介质基板，其特征在于，所述微波复合介质基板是根据权利要求1～4中任一项所述方法制备获得。
6.如权利要求5所述的微米级表面多孔型SiO2基微波复合介质基板，其特征在于，所述微波复合介质基板的介电常数为2.1～2.5，介电损耗为1.6×10-3～2.4×10-3，热膨胀系数为46～56ppm/℃。
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