CN107113969A - 陶瓷基板 - Google Patents

陶瓷基板 Download PDF

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CN107113969A
CN107113969A CN201680005732.7A CN201680005732A CN107113969A CN 107113969 A CN107113969 A CN 107113969A CN 201680005732 A CN201680005732 A CN 201680005732A CN 107113969 A CN107113969 A CN 107113969A
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ceramic layer
conductive pattern
ceramic substrate
silver
ceramic
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CN107113969B (zh
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加藤达哉
伊东正宪
沓名正树
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Niterra Co Ltd
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NGK Spark Plug Co Ltd
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Abstract

陶瓷基板具备主要由玻璃陶瓷形成的陶瓷层；和，主要由银(Ag)形成的导体图案，在与导体图案相邻的相邻区域中，陶瓷层中所含的硼原子(B)的浓度越接近导体图案越高。

Description

陶瓷基板
技术领域
本发明涉及一种陶瓷基板。
背景技术
已知陶瓷基板中具备主要由玻璃陶瓷形成的陶瓷层、和主要含有银(Ag)的导体图案。这样的陶瓷基板如下形成：在作为陶瓷层焙烧前的形态的生片上涂布作为导体图案焙烧前的形态的导体糊剂，然后进行焙烧，从而形成。这样的陶瓷基板也被称为低温共烧陶瓷(LTCC：Low Temperature Co-fired Ceramics)基板。
通过焙烧形成陶瓷基板时，由于导体糊剂的银成分向陶瓷层扩散，因此有时在陶瓷层中产生孔隙、变形、变色等。认为，银成分向陶瓷层的扩散被导体图案中所含的银成分的氧化促进。
专利文献1中公开了如下技术：将导体糊剂中所含的银粉末的表面用锑盐覆盖，从而抑制银成分向陶瓷层的扩散。专利文献2中公开了如下技术：在导体糊剂中添加硅粉末，从而抑制银成分向陶瓷层的扩散。
现有技术文献
专利文献
专利文献1：日本特开平6-252524号公报
专利文献2：日本特开2007-234537号公报
发明内容
发明要解决的问题
专利文献1、2的技术中，有时无法充分抑制银成分向陶瓷层的扩散。
用于解决问题的方案
本发明是为了解决上述课题而作出的，可以以以下的方案而实现。
(1)本发明的一个方案提供一种陶瓷基板，其具备：主要由玻璃陶瓷形成的陶瓷层；和，主要由银(Ag)形成的导体图案。该陶瓷基板中，在与前述导体图案相邻的相邻区域中，前述陶瓷层中所含的硼原子(B)的浓度越接近前述导体图案越高。根据该方案，可以抑制源自银成分的扩散而在陶瓷层中产生孔隙、变形、变色等。其结果，可以提高陶瓷基板的品质。
(2)上述方案的陶瓷基板中，相邻区域可以具有如下区域：其含有与位于陶瓷层中厚度方向的中央的中央区域相比成为3倍以上的浓度的硼原子(B)。根据该方案，可以充分抑制源自银成分的扩散而在陶瓷层中产生孔隙、变形、变色等。
(3)上述方案的陶瓷基板中，前述导体图案中可以存在有镧原子(La)和钛原子(Ti)中的至少一者。根据该方案，可以抑制源自银成分的扩散而在陶瓷层中产生孔隙、变形、变色等。
(4)上述方案的陶瓷基板中，前述陶瓷层可以包含硼硅酸盐玻璃和氧化铝(Al2O3)。根据该方案，可以提高硼硅酸盐玻璃系陶瓷基板的品质。
本发明不限定于陶瓷基板可以以各种方案实现，例如可以以制造陶瓷基板的制造方法、具备陶瓷基板的装置、制造陶瓷基板的制造装置等方案实现。
附图说明
图1为示意性示出陶瓷基板的截面的说明图。
图2为示出陶瓷基板的制造方法的工序图。
图3为示出评价试验的结果的表。
具体实施方式
A.实施方式
图1为示意性示出陶瓷基板110的截面的说明图。陶瓷基板110为低温共烧陶瓷(LTCC)基板。陶瓷基板110上形成有实现规定功能的电路的至少一部分。本实施方式中，陶瓷基板110上形成有以电子部件等传导信号的电路。
陶瓷基板110具备陶瓷层120和导体图案130。本实施方式中，陶瓷基板110具有如下结构：在相互层叠的陶瓷层120彼此之间形成有导体图案130。本实施方式中，陶瓷基板110上，除导体图案130之外设置有导通孔和通孔等(未作图示)作为构成电路的导体。其他实施方式中，陶瓷基板110中，2个以上的导体图案130可以与其他陶瓷层120一起进一步层叠。
陶瓷基板110的陶瓷层120具有电绝缘性。陶瓷层120主要由玻璃陶瓷形成。本说明书中，“主要由(成分)形成”是指，该成分占整体的50质量％以上。本实施方式中，陶瓷层120是将硼硅酸系玻璃粉末与氧化铝(Al2O3)粉末焙烧而成的陶瓷层。硼硅酸系玻璃主要由二氧化硅(SiO2)、氧化铝(Al2O3)和氧化硼(B2O3)形成。
陶瓷层120具有与导体图案130相邻的相邻区域121。陶瓷层120中所含的硼原子(B)的浓度在相邻区域121中越接近导体图案130越高。本实施方式中，相邻区域121具有如下区域：其含有硼原子(B)的浓度与位于陶瓷层120中厚度方向的中央的中央区域相比成为3倍以上的浓度的硼原子(B)。
陶瓷基板110的导体图案130主要由银(Ag)形成。本实施方式中，导体图案130含有银(Ag)粉末和硼硅酸系玻璃粉末，且具备导电性。本实施方式中，导体图案130中存在有镧原子(La)和钛原子(Ti)中的至少一者。本实施方式中，导体图案130的厚度约为10μm。
图2为示出陶瓷基板110的制造方法的工序图。首先，制作作为陶瓷层120焙烧前的状态的生片(工序P110)。
生片在无机成分的粉末中混合粘合剂(粘结剂)、增塑剂、溶剂等而成形为薄板状(片状)。本实施方式中，将作为无机成分的粉末的硼硅酸系玻璃粉末与氧化铝粉末以体积比60：40、以总量成为1kg的方式称量，然后将它们的粉末放入氧化铝制的容器(罐)中。之后，将作为粘合剂的120g的丙烯酸类树脂、作为溶剂的适量的甲乙酮(MEK)、和作为增塑剂的适量的邻苯二甲酸二辛酯(DOP)加入至罐内的材料。之后，用5小时将罐内的材料混合，从而得到陶瓷浆料。之后，利用刮刀法，自陶瓷浆料制作生片。本实施方式中，生片的厚度为0.15mm。本实施方式中，利用冲裁加工将生片成形。
制作生片(工序P110)，然后制作作为导体图案130焙烧前的状态的导体糊剂(工序P120)。作为导体图案130焙烧前的形态的导体糊剂是在银(Ag)粉末中添加金属硼化物的粉末而成的糊剂。
从抑制银向陶瓷层120的扩散的观点出发，导体糊剂中添加的金属硼化物优选为六硼化镧(LaB6)、六硼化硅(SiB6)和二硼化钛(TiB2)中的至少1个。从充分抑制银向陶瓷层120的扩散的观点出发，导体糊剂中所含的无机成分中的金属硼化物和金属硅化物的总含量优选为3体积％以上且9体积％以下。
本实施方式中，制作作为导体图案130焙烧前的状态的导体糊剂时，作为导体糊剂的无机成分材料，准备在作为导体材料的银(Ag)粉末中混合与陶瓷层120的成分共通的硼硅酸系玻璃粉末而成的混合粉末。之后，在无机成分的混合粉末中加入将金属硼化物的粉末、作为粘合剂的乙基纤维素、和作为溶剂的萜品醇。之后，使用三辊磨将材料混炼，从而得到导体糊剂。
制作导体糊剂(工序P120)，然后将导体糊剂涂布于生片(工序P130)。本实施方式中，通过丝网印刷将导体糊剂涂布于生片。
将导体糊剂涂布于生片(工序P130)，然后将涂布有导体糊剂的生片进行焙烧(工序P140)。由此，完成陶瓷基板110。
本实施方式中，在将生片进行焙烧前，制作层叠有多个生片的层叠体。本实施方式中，通过切削加工，将层叠体成形为适于焙烧的形状。本实施方式中，在250℃的大气中，将层叠体暴露10小时，从而将层叠体脱脂。本实施方式中，将层叠体脱脂后，在850℃的大气中，将层叠体暴露60分钟，从而将层叠体进行焙烧。经过这些工序得到陶瓷基板110。
将层叠体进行焙烧时，利用作为导体糊剂中所含的添加成分的金属硼化物的氧化反应，导体糊剂附近的氧被消耗。由此，导体糊剂中所含的银成分的氧化被抑制。因此，银成分向陶瓷层120的扩散被抑制。
在焙烧中作为氧化了的添加成分的金属硼化物的至少一部分向陶瓷层120中与导体图案130相邻的相邻区域121扩散。因此，陶瓷层120中所含的硼原子(B)的浓度在与导体图案130相邻的相邻区域121中，越接近导体图案130越高。从充分抑制银向陶瓷层120的扩散的观点出发，相邻区域121优选具有如下区域：其含有与陶瓷层120中位于厚度方向的中央的中央区域相比3倍以上的浓度的硼原子(B)。
在导体糊剂中添加六硼化镧(LaB6)时，导体图案130中存在有源自添加成分的镧原子(La)。在导体糊剂中添加二硼化钛(TiB6)时，导体图案130中存在有源自添加成分的钛原子(Ti)。
图3为示出评价试验的结果的表。图3的评价试验中，作为使用各不同的导体糊剂的陶瓷基板110，制作试样S01～S07。图3的表中，作为导体图案130焙烧前的状态的导体糊剂中的添加剂的含量表示陶瓷糊剂中所含的无机成分中的添加剂的体积百分率。
试样S01～S06的制造方法与图2的制造方法同样。试样S07的制造方法除不在导体糊剂中添加金属硼化物的方面之外，与图2的制造方法同样。
使用扫描型电子显微镜(SEM)和电子探针显微分析仪(EPMA)，对各试样的截面进行观察，从而测定硼(B)和银(Ag)向陶瓷层120的扩散距离。以位于陶瓷层120中厚度方向的中央的中央区域中的硼(B)浓度为基准值，在10处测定从陶瓷层120与导体图案130的界面至硼(B)浓度成为低于基准值的3倍的位置的距离作为硼的扩散距离。以陶瓷层120与导体图案130的界面中的银(Ag)浓度为基准值，在10处测定从该界面至陶瓷层120中银(Ag)浓度成为基准值的一半的位置的距离，将其平均值作为银的扩散距离而求出。
以如下基准判定各试样。
○(优)：银的扩散距离低于5μm
×(差)：银的扩散距离为5μm以上
根据试样S01～S06和试样S07的评价结果可知，在作为导体图案130焙烧前的形态的导体糊剂中添加作为金属硼化物的六硼化镧(LaB6)、六硼化硅(SiB6)和二硼化钛(TiB2)，从而可以抑制银向陶瓷层120的扩散。另外可知，作为导体图案130焙烧前的状态的导体糊剂中所含的无机成分中的金属硼化物的含量为3体积％以上且9体积％以下时，可以充分抑制银向陶瓷层120的扩散。另外可知，银向陶瓷层120的扩散被充分抑制时，陶瓷层120中，形成如下区域作为相邻区域121：其含有与位于厚度方向中央的中央区域相比成为3倍以上的浓度的硼原子(B)。
根据以上说明的实施方式，陶瓷基板110中，在与导体图案130相邻的相邻区域121中，陶瓷层120中所含的硼原子(B)的浓度越接近导体图案130越高。由此，可以抑制源自银成分的扩散而在陶瓷层120中产生孔隙、变形、变色等。其结果，可以提高陶瓷基板110的品质。
另外，相邻区域121具有如下区域：其含有与位于陶瓷层120中厚度方向的中央的中央区域相比成为3倍以上的浓度的硼原子(B)。因此，可以充分抑制源自银成分的扩散而在陶瓷层120中产生孔隙、变形、变色等。
B.其他实施方式
本发明不限定于上述实施方式、实施例、变形例，在不脱离其主旨的范围内可以以各种构成实现。例如，与发明内容的栏中记载的各方案中的技术特征对应的实施方式、实施例、变形例中的技术特征是为了解决上述课题的一部分或全部、或者为了达成上述效果的一部分或全部，而可以适当进行替换、组合。另外，该技术特征如果不是在本说明书中作为必须的特征而进行说明，则适当可以删除。
其他实施方式中，制作作为导体图案130焙烧前的状态的导体糊剂时(工序P120)，在原料粉末中加入粘合剂和溶剂前，在原料粉末中混合金属硼化物的粉末，从而可以使金属硼化物的粉末附着于银(Ag)粉末的表面。由此，可以进一步抑制银成分从导体图案130向陶瓷层120的扩散。
附图标记说明
110…陶瓷基板
120…陶瓷层
121…相邻区域
130…导体图案

Claims (4)

1.一种陶瓷基板，其特征在于，具备：
主要由玻璃陶瓷形成的陶瓷层、和
主要由银(Ag)形成的导体图案，
在与所述导体图案相邻的相邻区域中，所述陶瓷层中所含的硼原子(B)的浓度越接近所述导体图案越高。
2.根据权利要求1所述的陶瓷基板，其中，所述相邻区域具有如下区域：其含有与位于所述陶瓷层中厚度方向的中央的中央区域相比成为3倍以上的浓度的硼原子(B)。
3.根据权利要求1或权利要求2所述的陶瓷基板，其中，所述导体图案中存在有镧原子(La)和钛原子(Ti)中的至少一者。
4.根据权利要求1至权利要求3中任一项所述的陶瓷基板，其中，所述陶瓷层包含硼硅酸盐玻璃和氧化铝(Al2O3)。
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