CN1146055A - 用于氮化铝衬底的厚膜导体浆料组合物 - Google Patents
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Abstract
本发明涉及厚膜导体浆料组合物,可用厚膜技术将其加于氮化铝衬底上,可用丝网印刷或涂覆然后焙烧的方法在衬底上形成厚膜导体。将导体粉和硼化物分散于有机媒体中制成该组合物。
Description
本发明涉及厚膜导体浆料组合物。特别是涉及能用常规方法在氮化铝衬底上印刷膜的厚膜导体浆料组合物。
通常,厚膜导体浆料组合物包含导电组分,粘接剂和有机媒介物作为主要成分。广泛使用的导电组分有钯(Pd)、铂(Pt)和银(Ag)及其混合物的贵金属细粉,或铂和银的氧化物或其混合物。粘接剂采用玻璃粘接剂,并采用惰性液体作有机介质。
用丝网印刷法将这些厚膜导体浆料印刷到衬底上,并烧结印刷图形。常用氧化铝或氮化铝构成的陶瓷衬底作衬底。
近年来,由于氮化铝衬底有高导热系数,因此要求用氮化铝衬底作高温环境下使用的电路板。但是,为了将金属导体粘到氮化铝衬底上,必须采用厚膜技术,将原子形式的金属引入陶瓷衬底表面,这些原子形式的金属有极好的化学活性,与衬底表面上存在的多余氧化合,在金属与衬底之间形成薄反应层(氧化膜),通过该薄反应层金属导体粘到衬底上。脉冲调制累积法需要大而价格昂贵的设备,而且由于含有氮气或产生氧化氮,因而引起反应差等问题。因此,要求开发厚膜导体浆料组合物,用厚膜技术将它加到氮化铝衬底上,用丝网印刷法或涂覆法在氮化铝衬底上加厚膜导体组合物并随后焙烧,在衬底上形成“厚膜”导体。
本发明的目的是,提供可丝网印刷在氮化铝衬底上的厚膜导体浆料组合物,将导体粉和硼化物分散在有机媒体中形成该组合物。
本发明的另一目的是,提供可丝网印刷在氮化铝衬底上的厚膜导体浆料组合物。将导体粉和二元硼化物,金属硼或三元或多元的硼化物中的任何一种分散于有机媒体中形成该组合物。
此外,本发明的目的是,提供可丝网印刷在氮化铝衬底上的厚膜导体浆料组合物,用导体粉和选自TiB2、ZrB2、HfB2、UB2、NbB2、TaB2、CrB2、MoB2、W2B5、CaB6、SrB6、BaB6、LaB6、CeB6、PrB6、NdB6、SmB6、EuB6、Ni3B6,和Ni2B6中至少一种金属硼化物分散于有机媒体中制成该组合物。
图1是测试本发明的厚膜导体浆料的导电性所用的测试图形的平面图。
关键词:
1.测试图形
2.导体电阻值测试图形
3.盘
4.布线定位标记
5.布线
6.布线折弯标记
本发明的目的是提供厚膜导体浆料组合物,可用厚膜技术将其加到氮化铝衬底上,并可用丝网印刷或涂覆然后焙烧的方法将其在氮化铝衬底上形成“厚膜”导体。
本发明的另一目的是提供厚膜导体浆料组合物,可用厚膜技术将其加到氮化铝衬底上,并可用丝网印刷或涂覆然后焙烧的方法,将其在氮化铝衬底上形成“厚膜”导体,并可在所获得的导体表面上焊接或镀覆并保持良好的焊料浸润性。
能达到上述目的的按本发明一个实施例的厚膜导体浆料是可在氮化铝衬底上丝网印刷的,将导体粉和硼化物分散于有机媒体中而获得的厚膜导体浆料组合物。
本发明用的硼化物是包含硼和金属元素的化合物。这些化合物包括硼和金属元素的二元化合物,(称为金属硼化物),和三元或更多元的含硼化合物。它们包括在空气中在600-1000℃的温度范围内加热能生成硼酸的所有化合物。金属硼化物的例子包括TiB2、ZrB2、HfB2、UB2、NbB2、TaB2、CrB2、MoB2、W2B5、CaB6、SrB6、BaB6、LaB6、CeB6、PrB6、NdB6、SmB6、EuB6、Ni3B6,和Ni2B6。
本发明用硼化物基本上可包括那些在浆料焙烧工业中不会由硼形成B2O3而造成差的焊料浸润性变成玻璃化而覆盖导体表面的硼化物。能造成差的焊料浸润性的这种B2O3与用作导体的贵金属种类及其形式有关。即,无论是纯金属或合金,应能控制焙烧后的厚膜密度。而且,由于生成的B2O3变成厚膜表面中玻璃化,因而阻止B2O3沉淀(生成的B2O3量也随硼化物种类变化)。因此,可在较宽范围内选择硼化物含量。
例如,在本发明中用ZrB2硼化物时,ZrB2的含量不能大于以银导体重量为基的1.6wt%,以使本发明的厚膜导体浆料组合物用于氮化铝衬底不会引起差的焊料浸润性。
本发明用的导体粉可以是任何贵金属粉。通常,可用所有贵金属。但特别是可用金、银、铂、钯、铑和它们的混合物或它们的合金。用这些金属或它们的合金的细粉。只要它适合所使用的方法,金属粉的颗粒直径不特别重要。
本发明中,上述导电粉与硼化物分散于有机媒体中制成称为“浆料”的,有半流动态的软化度的分散体。
本发明的厚膜浆料中的有机媒体与分散体中的无机固体物之比与浆料使用方法和所用有机媒体的种类有关,而且是可变的。
通常,为了获得好的涂覆性,分散体包含50-90wt%的无机固体物,10-50wt%的有机媒体。
可用全部惰性液体作有机媒体。加或不加增厚剂和/或其它公用添加剂的水或任何一种有机液体均可用作有机媒体。能用的有机媒体的实例包括脂族醇类,这些醇类的酯类,如乙酸酯和丙酸酯,萜烯类,如松节油,松油醇等,树脂类的溶液,如在诸如松节油和乙二醇单乙酸酯的单丁基醚的溶剂中加低醇的聚甲基丙烯酸酯制成的溶液。有机媒体中或由这些化合物制成的有机媒体中可包含将其加于衬底后允许迅速固化的挥发性液体。
以乙基纤维素和β-松油醇为基的有机媒体最佳。
本发明中,上述浆料组合物中还可加入玻璃粘接剂。对所用玻璃粘接剂中玻璃本身的组分设有严格规定。在烧工艺中不与上述的导体相和硼化物反应,其热膨胀系数与氮化铝衬底适应,有足够的粘度,在烧结温度玻璃流动促进金属颗粒烧结的任何玻璃粘接剂均可用。有共同的玻璃形成特性和玻璃改性化合物的玻璃氧化物类的硼化物范围的实例包括硼硅酸铝。如硼硅酸铅的硅酸铅和硅酸铅本身;和硅酸鉍。
玻璃粘接剂的颗粒直径没有特别严格规定。但是,玻璃颗粒的直径范围是0.1到10μm,最好是0.5-5μm,平均颗粒直径密度2-3μm。为了在印刷浆料时有合适的流动性,要求用有极大表面积的颗粒直径小于0.1μm的细玻璃和大量有机媒体。但是若颗粒直径大于10μm,在后面会妨碍丝网印刷。
烧结工艺中氧化生成的金属氧化物和B2O3与氮化铝衬底反应生成的氧化反应产物2Al2O3 B2O3有助于提高金属,或导体与衬底之间的粘接力。
用带有图1所示导体电阻值测试图形2和焊盘(2×2mm)3的测试图形1,厚膜浆料组合物丝网印刷在铝衬底上,干燥并焙烧。焙烧后的导体厚度约10μm。
1.测试电阻值
测N次(N=4)导体电阻测试图形2的电阻值。用200除平均值,确定每单位表面积的电阻值,然后,按测得的膜厚确定每10μm厚的膜的单位表面电阻值(单位:欧姆/方)。
2.粘接强度
三根回形针形的布线5按测试图形1上设置的布线定位标记4搭接到图1所示的9个焊盘(2mm×2mm)3上。并在220℃±5℃的温度焊接该状态。所用焊料组分是锡/铅/银=62/36/2。焊接后,使其经16小时冷却到室温,并按折弯标记6在底部将布线每折90°,测N次(N=12)的抗拉强度。这里用N=12,用12次测试平均值为加到衬底上的厚膜导体的粘接强度。
3.焊料浸润
将图1的测试图形浸入焊料中5次(与测粘接强度用的次数相同)。然后取出、观察焊料粘到焊盘3的状态。
用焊料完全粘接到焊盘上而看不到导体表面的焊盘数与总焊盘数之比来测试。本发明的情况下,比例为90%时认为是好的。
实施例
现在用实施例和对比例更详细地说明本发明。这些实施例中,导体粉、金属硼化物和有机媒体的混合比按重量百分比(wt%)示于表1中。
实施例1-10
银粉,硼化锆和有机媒体按表1所列重量比混合,然后,用三辊球磨机搅拌均匀,获得厚膜导体浆料的分散体。调节荻得的浆料组合物的流动性使其满足丝网印刷要求。
以上调节过的厚膜浆料组合物用丝网印刷法加到氮化铝衬底上,并对印成的图形在850℃下焙烧,制成本发明的厚膜导体,这些导体焙烧后的厚度是10μm。
用上述方法评估这些导体的电阻值,粘接强度,和焊料浸润性,结果列于表1中。
实施例11
银粉、硼化锆和表2所列级分的玻璃粘接剂按表1所示比例分散于包含乙基纤维素和β-松节油的有机媒体中,然后,用三辊球磨机搅拌,制成浆料组合物。用实施例1-10中相同的方法制成厚膜导体。测试其性能、列于表1中。
比较例
按实施例1-11的方法制备比较例的浆料组合物、只是不包含硼化物、按表1所列重量比将银粉分散于有机媒体中,并用三辊球磨机搅拌。用实施例中同样的方法将浆料组合物加到氮化铝衬底上。按实施例1的方法测试衬底上形成的厚膜浆料的电阻值,粘接强度和焊料浸润性、结果列于表1中。
表1实施例
对比例 1 2 3 4 5 6 7 8 9 10 11导体Ag(wt%) 84.2 83.3 83.1 82.4 81.3 79.5 77.7 72.1 67.2 63.0 59.3 83.2硼化物ZrB2(wt%) 0 1.0 1.3 2.2 3.5 5.6 7.8 14.4 20.2 25.2 29.6 0.6玻璃(wt%) 0 0 0 0 0 0 0 0 0 0 0 0.6有机媒体(wt%)乙基纤维素的β-松油醇溶液(为了具有能丝 15.8 15.7 15.6 15.4 15.2 14.9 14.6 13.5 12.6 11.8 11.1 15.6网印刷的粘度这里适当加入β-松油醇)焙烧温度(℃) 850 850 850 850 850 850 850 850 850 850 850 850性能:1.电阻值(mΩ/方, 2.1 2.1 3.4 3.6 3.8 4.8 5.6 11.0 27.0 57.0 69.9 3.3
10μm厚)2.粘接强度(牛顿) 0 20 24 - - - - - - - - 203.焊料浸润性 好 好 好 差 差 差 差 差 差 差 差 好
按本发明的厚膜导体浆料组合物能用厚膜技术加到氮化铝衬底上,能用丝网印刷或涂覆然后焙烧的方法在衬底上形成粘接牢固的厚膜导体,也可在衬底上形成的导体表面上加焊或焊料镀层。
Claims (5)
1.厚膜导体浆料组合物,能用丝网印刷法将其加于氮化铝衬底上,其中将导体粉和硼化物分散于有机媒体中制成该组合物。
2.厚膜导体浆料组合物,能用丝网印刷法将其加于氮化铝衬底上,其中将导体粉和硼与金属元素的二元化合物或三元或更多元的含硼化合物分散于有机媒体中制成该组合物。
3.厚膜导体浆料组合物,能用丝网印刷法将其加于氮化铝衬底上,其将导体粉和选自TiB2、ZrB2、HfB2、UB2、NbB2、TaB2、CrB2、MoB2、W2B5、CaB6、SrB6、BaB6、LaB6、CeB6、PrB6、NdB6、SmB6、EuB6、Ni3B6和Ni2B6中至少一种金属硼化物分散于有机媒体中制成该组合物。
4.按权利要求3的组合物,其特征是,所述金属硼化物是ZrB2。
5.按权利要求4的组合物,其特征是,所述导电粉是银粉,ZnB6的用量不超过银粉重量为基的1.6wt%。
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JP22963595A JP3927250B2 (ja) | 1995-08-16 | 1995-08-16 | 窒化アルミニウム基板用厚膜導体ペースト組成物 |
JP229635/95 | 1995-08-16 |
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CN1146055A true CN1146055A (zh) | 1997-03-26 |
CN1096685C CN1096685C (zh) | 2002-12-18 |
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CN96110998A Expired - Fee Related CN1096685C (zh) | 1995-08-16 | 1996-08-16 | 用于氮化铝衬底的厚膜导体浆料组合物 |
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US (1) | US6103146A (zh) |
EP (1) | EP0764618B1 (zh) |
JP (1) | JP3927250B2 (zh) |
KR (1) | KR100215186B1 (zh) |
CN (1) | CN1096685C (zh) |
DE (1) | DE69624435T2 (zh) |
TW (1) | TW445461B (zh) |
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CN111584367A (zh) * | 2020-04-09 | 2020-08-25 | 项兴秀 | 厚膜电路印刷用于半导体封装玻璃制作的方法 |
CN113470865A (zh) * | 2021-09-06 | 2021-10-01 | 西安宏星电子浆料科技股份有限公司 | 一种氮化铝用环保型银导体浆料 |
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- 1996-08-01 EP EP96112439A patent/EP0764618B1/en not_active Expired - Lifetime
- 1996-08-14 KR KR1019960033781A patent/KR100215186B1/ko not_active IP Right Cessation
- 1996-08-16 CN CN96110998A patent/CN1096685C/zh not_active Expired - Fee Related
- 1996-09-05 TW TW085110875A patent/TW445461B/zh not_active IP Right Cessation
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Cited By (4)
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CN104952507A (zh) * | 2014-03-27 | 2015-09-30 | 浙江德汇电子陶瓷有限公司 | 导电组合物和导电浆料和线路板及其制造方法 |
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CN111584367B (zh) * | 2020-04-09 | 2023-02-28 | 浙芯紫外半导体科技(杭州)有限公司 | 厚膜电路印刷用于半导体封装玻璃制作的方法 |
CN113470865A (zh) * | 2021-09-06 | 2021-10-01 | 西安宏星电子浆料科技股份有限公司 | 一种氮化铝用环保型银导体浆料 |
Also Published As
Publication number | Publication date |
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TW445461B (en) | 2001-07-11 |
KR100215186B1 (ko) | 1999-08-16 |
EP0764618A2 (en) | 1997-03-26 |
DE69624435D1 (de) | 2002-11-28 |
EP0764618A3 (en) | 1997-06-04 |
EP0764618B1 (en) | 2002-10-23 |
DE69624435T2 (de) | 2003-06-18 |
CN1096685C (zh) | 2002-12-18 |
US6103146A (en) | 2000-08-15 |
JP3927250B2 (ja) | 2007-06-06 |
KR970012797A (ko) | 1997-03-29 |
JPH0952785A (ja) | 1997-02-25 |
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