CN114773056A - 一种npo mlcc用陶瓷材料的助烧剂、陶瓷材料及制备方法 - Google Patents

一种npo mlcc用陶瓷材料的助烧剂、陶瓷材料及制备方法 Download PDF

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CN114773056A
CN114773056A CN202210506570.2A CN202210506570A CN114773056A CN 114773056 A CN114773056 A CN 114773056A CN 202210506570 A CN202210506570 A CN 202210506570A CN 114773056 A CN114773056 A CN 114773056A
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sintering aid
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黄正信
李英杰
林文忠
詹振豪
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Lizhi Electronics Nantong Co ltd
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Abstract

本发明公开了一种NPO MLCC用(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料的助烧剂、NPO MLCC用陶瓷材料及制备方法。助烧剂包括以下重量百分比的成分：SiO23~4%、MnCO310~15%、LiCO35~10%、Nb2O515~20%、CaCO325~30%、SrCO325~30%、TiO21~5%和ZnO 1~5%。将(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3粉体与助烧剂粉体按照不同比例混合、球磨、烘干得到混合粉末；在所述混合粉末中加入黏结剂，造粒、过筛、成型、涂覆铜电极、排胶后，于氮气气氛910~1040℃的温度下烧结得到NPO MLCC用陶瓷材料。本发明的(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料的烧结温度降低至1000℃，可与铜内电极进行共烧；制备出的陶瓷材料的宽温稳定性能好，介电损失低，体系不含鉛，具有良好的应用前景。

Description

一种NPO MLCC用陶瓷材料的助烧剂、陶瓷材料及制备方法
技术领域
本发明涉及一种NPO MLCC(片式多层陶瓷电容器，Multi-layer CeramicCapacitors)用(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料的助烧剂、包含该助烧剂的NPO MLCC用陶瓷材料及其制备方法，属于陶瓷电容器领域。
背景技术
随着终端设备轻薄化和功能完善化的市场需求，目前以陶瓷为基础的电子零组件发展趋势主要有：(1)往更小尺寸、更多层数及更大单位体积电容值发展，以满足电子产品追求轻薄短小及增加功能密度的发展趋势；然而高容积层陶瓷电容器的发展趋势，不是如何增加电容值，而是从降低介电厚度着手；(2)往模块化发展，将主动组件、小型被动组件整合于单一模块中，以减少被动组件的数目及面积，降低成本，并提高性能表现与可靠度；(3)往高频化化发展，由于电子产品所使用的带宽愈来愈高，相同的，被动组件亦须符合高频电子产品的需求。
其中NPO为不受温度影响的电容器，在温度-55℃～+125℃范围内的电容温度系数介于+30ppm～-30ppm之间。NPO电容值较小，最大为1μF左右，最小可低于1pF，NPO通常在高频范围使用。在制造高频积层结构组件时，内导体金属必须能与陶瓷介电材料共烧，而这限制了所能选用的内导体金属材料。为了符合在高频下具有高质量因素(Quality Factor,Q)的需求，选择高导电性电极材料并搭配积层陶瓷组件结构，制作成表面平整的高致密金属膜，是维持其高频特性的基本方法。银与金的导电性最好，但价格昂贵，一般常用铜与镍。此外，虽然采用纯银作为内电极为最佳选择，其有着最低的电阻值，但在高湿以及高偏压(Bias)下，易造成电子迁移(Electromigration)以及与焊锡接合时易造成SolderLeaching效应。
(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3具有高介电常数(εr)、低损耗(tanδ)和低谐振频率温度系数(τf)，可以用作微波频率下的介电谐振器，介电谐振器可用于微波滤波器和微波集成电路中的振荡稳定。用于微波的介电材料应具有合适的介电常数(εr)25～100、低介电损失(tanδ)<6E-04、高质量因子>10000和低的谐振频率温度系数(τf)0±20ppm/℃；但(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷烧结温度较高(>1350℃)，在实际应用上必须使用镍(熔点1455℃)或银钯电极(熔点1400℃)，而使用镍或银钯电极却会造成Q值下降。以铜作为内电极具有低价格优势、高传导性、无电迁移以及较不会造成Solder Leaching效应。因此如何降低烧结温度(<1050℃)使其与铜电极共烧是亟待解决的问题。
发明内容
本发明的目的在于提供一种NPO MLCC用(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料的助烧剂、NPO MLCC用陶瓷材料及其制备方法，以解决现有技术中(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料烧结温度过高无法与铜电极共烧的问题。
为实现上述目的，本发明采用如下技术方案：
一种NPO MLCC用(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料的助烧剂，所述陶瓷材料为(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3，所述助烧剂包括以下重量百分比的成分：SiO2 3～4％、MnCO310～15％、LiCO3 5～10％、Nb2O515～20％、CaCO3 25～30％、SrCO3 25～30％、TiO2 1～5％和ZnO1～5％。
在一优选实施例中，所述助烧剂包括以下重量百分比的成分：SiO2 3.3％、MnCO311.2％、LiCO3 7.4％、Nb2O5 16.5％、CaCO3 27.4％、SrCO3 28.2％、TiO2 1.7％和ZnO4.3％。
在一优选实施例中，所述助烧剂包括以下重量百分比的成分：SiO2 3％、MnCO315％、LiCO3 5％、Nb2O5 15％、CaCO3 30％、SrCO330％、TiO2 1％和ZnO 1％。
在一优选实施例中，所述助烧剂包括以下重量百分比的成分：SiO2 4％、MnCO310％、LiCO3 10％、Nb2O5 20％、CaCO3 25％、SrCO325％、TiO2 1％和ZnO 5％。
本发明还提供了一种NPO MLCC用陶瓷材料，包含(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基体材料和前述的助烧剂，所述助烧剂占陶瓷材料的重量百分比为1-5％。
优选地，所述助烧剂占陶瓷材料的重量百分比为3％。
其中，所述陶瓷材料在温度-55℃～125℃范围内的容温变化率≤0.003％，介电常数为26.4～33.4，介电损失为0.0005～0.01，绝缘阻抗为5E+07～4E+13。
本发明还提供了一种NPO MLCC用陶瓷材料的制备方法，包括：
将(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3粉体与助烧剂粉体按照前述比例混合、球磨、烘干得到混合粉末；
在所述混合粉末中加入黏结剂，造粒、过筛、成型、涂覆铜电极、排胶后，于氮气气氛950～1000℃的温度下烧结得到NPO MLCC用陶瓷材料。
本发明所达到的有益技术效果：通过将本发明的助烧剂添加至(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料，能够成功地将(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料的烧结温度降低至低于1000℃，可在氮气气氛下实现与纯铜进行共烧；制备出的陶瓷材料的温度稳定性在-55℃～125℃范围内满足容温变化率≤0.003％，介电常数最大可以达到>32，介电损失最小可以达到<0.0006，绝缘阻抗可以达到>1E+13，体系不含鉛，具有良好的应用前景。
附图说明
图1是实施例1中助烧剂含量分别为0wt％、1wt％、3wt％、5wt％的(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3陶瓷样品在烧结温度950℃下烧成的XRD图谱；
图2是实施例2中助烧剂含量分别为0wt％、1wt％、3wt％、5wt％的(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3陶瓷样品在烧结温度1000℃下烧成的XRD图谱；
图3是分别在烧结温度950℃(实施例1)、1000℃(实施例2)下制备的(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料的烧结密度随助烧剂含量变化图；
图4是分别在烧结温度950℃(实施例1)、1000℃(实施例2)下制备的(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料的烧结收缩率随助烧剂含量变化图；
图5是分别在烧结温度950℃(实施例1)、1000℃(实施例2)下制备的(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料的绝缘阻抗随助烧剂含量变化图；
图6是分别在烧结温度950℃(实施例1)、1000℃(实施例2)下制备的(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料的介电常数随助烧剂含量变化图；
图7是分别在烧结温度950℃(实施例1)、1000℃(实施例2)下制备的(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料的介电损失随助烧剂含量变化图；
图8是实施例1中助烧剂含量分别为0wt％、1wt％、3wt％、5wt％的(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料在烧结温度1000℃下烧成的容温变化率图；
图9是实施例1中不同助烧剂含量的(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料在烧结温度950℃下烧成的SEM图，其中(a)不含助烧剂，(b)助烧剂含量1wt％，(c)助烧剂含量3wt％，(d)助烧剂含量5wt％；
图10是实施例2中不同助烧剂含量的(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料在烧结温度1000℃下烧成的SEM图，其中(a)不含助烧剂，(b)助烧剂含量1wt％，(c)助烧剂含量3wt％，(d)助烧剂含量5wt％；
图11是实施例3中助烧剂含量分别为0wt％、1wt％、3wt％、5wt％的(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料在烧结温度1000℃下烧成的容温变化率图；
图12是实施例4中助烧剂含量分别为0wt％、1wt％、3wt％、5wt％的(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料在烧结温度1000℃下烧成的容温变化率图。
具体实施方式
下面结合具体实施例对本发明作进一步描述。以下实施例仅用于更加清楚地说明本发明的技术方案，而不能以此来限制本发明的保护范围。
实施例1
在本实施例中，使用的助烧剂成分及重量百分比如下：SiO23.3％、MnCO3 11.2％、LiCO3 7.4％、Nb2O5 16.5％、CaCO3 27.4％、SrCO3 28.2％、TiO2 1.7％和ZnO 4.3％。
将(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3粉体与上述助烧剂粉体按照分别不同比例：助烧剂含量为0wt％、1wt％、3wt％、5wt％，进行混合、球磨、烘干得到混合粉末；
在得到的混合粉末中加入黏结剂造粒，造粒完成后使粉料过200目筛，成型、涂覆铜电极、排胶后，于氮气气氛中950℃的温度下烧结并保温2h，得到助烧剂含量分别为0wt％、1wt％、3wt％、5wt％的陶瓷材料。
实施例2
在本实施例中，助烧剂成分及重量百分比同实施例1。
将(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3粉体与上述助烧剂粉体按照分别不同比例：助烧剂含量为0wt％、1wt％、3wt％、5wt％，进行混合、球磨、烘干得到混合粉末；
在得到的混合粉末中加入黏结剂造粒，造粒完成后使粉料过200目筛，成型、涂覆铜电极、排胶后，于氮气气氛中1000℃的温度下烧结并保温2h，得到助烧剂含量分别为0wt％、1wt％、3wt％、5wt％的陶瓷材料。
对实施例1和实施例2制备的各陶瓷材料试样进行微波介电性能、X射线衍射分析(XRD)和扫描电镜分析(SEM)测试。
图1为不同助烧剂含量的陶瓷样品在烧结温度950℃下烧成的XRD图谱，图2为实施例2制备的不同助烧剂含量的陶瓷样品在烧结温度1000℃下烧成的XRD图谱。从图1和图2中可以看出，即使助烧剂含量增加到5％，在950℃至1000℃的温度下烧成的陶瓷也不会产生二次相，因此，助烧剂的加入不会影响(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3陶瓷相结构或导致杂相生成。
图4是不同烧结温度下制备的(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料的烧结收缩率随助烧剂含量变化图。由图中可以看出，与不含助烧剂相比，在950℃和1000℃的温度下，添加助烧剂均可以有效的提高陶瓷体烧结收缩率，且陶瓷收缩率随着助烧剂含量的增加呈上升趋势，当助烧剂含量增加到3％-5％时，陶瓷收缩率几乎达到最大。
图3为不同烧结温度下制备的(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料的烧结密度随助烧剂含量变化曲线图。从图3可以看出，其变化趋势与烧结收缩率曲线基本一致，与不含助烧剂相比，助烧剂的添加可以明显提高陶瓷体烧结密度，且烧结密度随着助烧剂含量的增加呈上升趋势，当助烧剂含量增加到3％或更多，烧结密度趋向平缓甚至有变小的趋势。
图9和图10分别是不同助烧剂含量的(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料在烧结温度950℃、1000℃下烧成的SEM图。其中，图9(a)和图10(a)是不含助烧剂的陶瓷体的SEM图，图9(b-d)和图10(b-d)是含有助烧剂的陶瓷体的SEM图。从图9和图10均可以看出，不含助烧剂的陶瓷体不致密，而添加助烧剂后的陶瓷体密度显著提升。
图5是不同烧结温度制备的(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料的绝缘阻抗随助烧剂含量变化图。由图5可以看出，与不含助烧剂的陶瓷体相比，助烧剂的添加可以提高陶瓷体的绝缘阻抗，在1000℃的烧结温度下，绝缘阻抗可以达到>1E+13。
图6是不同烧结温度下制备的(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料的介电常数随助烧剂含量变化图。由图6可以看出，与不含助烧剂的陶瓷体相比，助烧剂的添加可以显著提高陶瓷体的介电常数，当助烧剂含量在3％-5％时，介电常数达到最大(>32)。
图7是不同烧结温度下制备的(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料的介电损失随助烧剂含量变化图。从图7可以看出，与不含助烧剂的陶瓷体相比，助烧剂的添加可以显著降低陶瓷体的介电损失，当烧结温度为950℃、助烧剂含量为3％时，介电损失最小(<0.0006)。
图8是助烧剂含量分别为0wt％、1wt％、3wt％、5wt％的(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料在烧结温度1000℃下烧成的容温变化率图。从图中可以看出，添加助烧剂的陶瓷体TCC符合NPO规范，在温度-55℃～125℃范围内的容温变化率≤0.003％。
实施例3
在本实施例中，助烧剂由以下重量百分比的成分构成：SiO2 3％、MnCO3 15％、LiCO3 5％、Nb2O5 15％、CaCO3 30％、SrCO3 30％、TiO21％和ZnO 1％。
将(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3粉体与上述助烧剂粉体按照分别不同比例：助烧剂含量为0wt％、1wt％、3wt％、5wt％，进行混合、球磨、烘干得到混合粉末；
在得到的混合粉末中加入黏结剂造粒，造粒完成后使粉料过200目筛，成型、涂覆铜电极、排胶后，于氮气气氛中1000℃的温度下烧结并保温2h，得到助烧剂含量分别为0wt％、1wt％、3wt％、5wt％的陶瓷材料。
实施例4
在本实施例中，助烧剂由以下重量百分比的成分构成：SiO2 4％、MnCO3 10％、LiCO3 10％、Nb2O5 20％、CaCO3 25％、SrCO3 25％、TiO2 1％和ZnO 5％。
将(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3粉体与上述助烧剂粉体按照分别不同比例：助烧剂含量为0wt％、1wt％、3wt％、5wt％，进行混合、球磨、烘干得到混合粉末；
在得到的混合粉末中加入黏结剂造粒，造粒完成后使粉料过200目筛，成型、涂覆铜电极、排胶后，于氮气气氛中1000℃的温度下烧结并保温2h，得到助烧剂含量分别为0wt％、1wt％、3wt％、5wt％的陶瓷材料。
对实施例3和实施例4烧成的各陶瓷材料试样进行微波介电性能测试，测试结果见表1。
表1实施例3与实施例4对应陶瓷样品电性能
Figure BDA0003637546910000101
从表1可以看出，在实施例3和实施例4组成范围中，与不含助烧剂的陶瓷相比，添加助烧剂可以提高陶瓷体烧结密度与烧结收缩率，且皆可以有效的提高介电常数，降低介电损失并提高绝缘阻抗。
图11和图12是实施例3和实施例4助烧剂含量分别为0wt％、1wt％、3wt％、5wt％的(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料在烧结温度1000℃下烧成的容温变化率图。从图中可以看出，TCC在实施例3符合NPO规范，而实施例4则需添加助烧剂至5wt％才符合NPO规范。
以上已以较佳实施例公布了本发明，然其并非用以限制本发明，凡采取等同替换或等效变换的方案所获得的技术方案，均落在本发明的保护范围内。

Claims (8)

1.一种NPO MLCC用(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料的助烧剂，其特征在于，所述助烧剂包括以下重量百分比的成分：SiO2 3~4% 、MnCO3 10~15 %、LiCO3 5~10 %、Nb2O5 15~20 %、 CaCO3 25~30 %、SrCO3 25~30 %、TiO2 1~5 %和ZnO 1~5 %。
2.根据权利要求1所述的一种NPO MLCC用(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料的助烧剂，其特征在于，所述助烧剂包括以下重量百分比的成分：SiO2 3.3%、MnCO3 11.2%、LiCO37.4%、Nb2O5 16.5%、 CaCO3 27.4%、SrCO328.2%、TiO2 1.7%和ZnO 4.3%。
3.根据权利要求1所述的一种NPO MLCC用(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料的助烧剂，其特征在于，所述助烧剂包括以下重量百分比的成分：SiO2 3%、MnCO3 15%、LiCO3 5%、Nb2O5 15%、 CaCO3 30%、SrCO3 30%、TiO2 1%和ZnO 1%。
4.根据权利要求1所述的一种NPO MLCC用(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基陶瓷材料的助烧剂，其特征在于，所述助烧剂包括以下重量百分比的成分：SiO2 4% 、MnCO3 10%、LiCO310%、Nb2O5 20%、 CaCO3 25%、SrCO325%、TiO2 1%和ZnO 5%。
5.一种NPO MLCC用陶瓷材料，其特征在于，包含 (Ca0.6Sr0.4)(Zr0.96Ti0.04)O3基体材料和权利要求1-4任一项所述的助烧剂，所述助烧剂占陶瓷材料的重量百分比为1-5%。
6.根据权利要求5所述的一种NPO MLCC用陶瓷材料，其特征在于，所述助烧剂占陶瓷材料的重量百分比为3%。
7.根据权利要求5所述的一种NPO MLCC用陶瓷材料，其特征在于，所述陶瓷材料在温度-55oC~125oC范围内的容温变化率≤0.003%，介电常数为26.4~33.4，介电损失为0.0005~0.01，绝缘阻抗为5E+07~4E+13。
8.权利要求5所述的NPO MLCC用陶瓷材料的制备方法，其特征在于，包括：
将(Ca0.6Sr0.4)(Zr0.96Ti0.04)O3粉体与助烧剂粉体按照权利要求5所述比例混合、球磨、烘干得到混合粉末；
在所述混合粉末中加入黏结剂，造粒、过筛、成型、涂覆铜电极，排胶后，于氮气气氛950~1000℃的温度下烧结得到NPO MLCC用陶瓷材料。
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