CN109285819A - 散热基板 - Google Patents

散热基板 Download PDF

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CN109285819A
CN109285819A CN201711205388.9A CN201711205388A CN109285819A CN 109285819 A CN109285819 A CN 109285819A CN 201711205388 A CN201711205388 A CN 201711205388A CN 109285819 A CN109285819 A CN 109285819A
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heat
radiating substrate
electric insulation
insulation layer
substrate according
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陈国勋
柯孟君
沙益安
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Polytronics Technology Corp
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Abstract

本发明提供一种散热基板包括金属基底、导热电绝缘层和金属层的层叠结构。该导热电绝缘层设置于该金属基底上，且该金属层设置于该导热电绝缘层上。该导热电绝缘层包含高分子聚合物以及散布于该高分子聚合物中的非圆球形导热填料。该高分子聚合物包含至少两种不同环氧当量的直链型环氧树脂，该非圆球形导热填料的平均粒径和比表面积的乘积在7.5～15μm·m2/g。该导热电绝缘层的玻璃转换温度在40～90℃，导热率1～6W/m·K。

Description

散热基板
技术领域
本发明涉及一种散热基板，尤其涉及一种使用金属基底的散热基板。
背景技术
一直以来，作为电子零件安装用散热基板，多使用金属芯基板，该金属芯基板是层合电绝缘材料层于金属板之上，并于电绝缘材料层之上形成铜箔，该铜箔形成布线图型。然后于布线图型上使用焊锡，来安装各种芯片，如芯片零件、硅半导体、端子等。
作为前述电绝缘材料层，例如添加无机填料于热可塑性聚酰亚胺或聚苯醚(PPE)。但是这样的热可塑性聚酰亚胺、PPE之类一般的树脂，因为树脂本身的热传导率低，所以要作为具有高散热性的电子零件用的散热基板有其困难。因此，近年来已对电绝缘材料层的高热传导化进行研究，例如使用结晶化树脂或高热传导性填料来作为提高树脂的热传导性的手段。
在车用市场或其他严酷环境，因可能于高温下曝晒及于酷寒环境中使用，该严苛使用环境对产品耐用度带来严峻考验。散热基板在上述严苛的高低温环境中使用，用来固定连接芯片的焊锡有时会因膨胀收缩的关系产生锡裂，严重影响芯片使用上的稳定度和可靠度。本发明是改善上述问题点，并考虑操作上的实用性，从而提供一种高可靠度的散热基板。
发明内容
为了解决上述问题，本发明的主要目的在于提供一种金属基底的散热基板，通过其中导热电绝缘层材料的改良，可提升于高低温环境中使用的稳定度，避免锡裂的问题。另外，本发明的散热基板改良其表面的金属层，进一步提升其剥离强度。
根据本发明的一实施例，一散热基板为包括金属基底、导热电绝缘层和金属层的层叠结构。该导热电绝缘层设置于该金属基底上，且该金属层设置于该导热电绝缘层上。该导热电绝缘层包含高分子聚合物以及散布于该高分子聚合物中的非圆球形导热填料。该高分子聚合物包含至少两种不同环氧当量的直链型环氧树脂，该非圆球形导热填料的平均粒径和比表面积(BET surface area)的乘积在7.5～15μm·m2/g。该导热电绝缘层的玻璃转换温度在40～90℃，导热率1～6W/m·K。
一实施例中，该非圆球形导热填料占该导热电绝缘层的体积百分比35～65％。
一实施例中，该非圆球形导热填料选自氧化铝、氮化铝、氮化硼、碳化硅或其组合。
一实施例中，该非圆球形导热填料包含破碎形导热填料。
一实施例中，至少两种不同环氧当量的直链型环氧树脂的平均环氧当量(EpoxyEquivalent Weight；EEW)为400～2000g/eq。
一实施例中，至少两种不同环氧当量的直链型环氧树脂的平均环氧当量为800～1500g/eq。
一实施例中，至少两种不同环氧当量的直链型环氧树脂中的一种直链型环氧树脂的环氧当量为100～400g/eq，另一种直链型环氧树脂的环氧当量为1500～4000g/eq。
一实施例中，至少两种不同环氧当量的直链型环氧树脂中至少一种直链型环氧树脂的EEW为100～500g/eq，且占该高分子聚合物的重量百分比大于20％。
一实施例中，该金属层包含一镀层，该镀层材料可以为锌、铬、镍或其组合，且镀层部分接触该导热电绝缘层。
一实施例中，该金属层包含镀镍铜箔，且镀镍部分接触该导热电绝缘层。
一实施例中，该散热基板经高压蒸煮2atm 121℃饱和蒸气96小时处理，该金属层的剥离强度降低率在30％之内。
一实施例中，该导热电绝缘层还包含潜变型硬化剂。
一实施例中，该潜变型硬化剂包含胺加成物(amine adduct)、酰肼(hydrazide)、二酰肼(dihydrazide)、二氰胺复合物(Dicy)、己二酸二酰肼(adipic acid dihydrazide)以及间苯二甲酸二酰肼(isophthalic dihydrazide)中至少一成分。
一实施例中，该胺加成物使用咪唑化合物(imidazole compound)、含有3级胺基的化合物(tertiary amino group-containing compound)或酰肼化合物(hydrazidecompound)与环氧化合物(epoxy compound)或异氰酸酯化合物(isocyanate compound)反应而成。
一实施例中，该散热基板在30℃环境下经过3个月后其粘度增加不超过1倍。
本发明的散热基板中的导热电绝缘层中选用至少两种不同环氧当量的直链型环氧树脂且特别选用非圆球形导热填料。因直链型环氧树脂相较于侧链型环氧树脂较软，故有助于防止锡裂。非圆球形导热填料因为整体的表面积增大，可以减少导热填料的使用比例而降低材料的硬度，因而也有助于防止锡裂发生。
另外，搭配潜变型硬化剂，将导热电绝缘层或其中高分子聚合物的玻璃转换温度控制在较低温的40～90℃(高于90℃容易产生锡裂问题，低于40℃时，高压蒸煮金属层剥离强度不佳)，可有效避免散热基板固定连接芯片的焊锡有时会因在高低温环境中使用因膨胀收缩进而产生锡裂的问题。
附图说明
图1为本发明一实施例的散热基板。
图2和图3为本发明散热基板测试锡裂的方式。
附图标记如下：
10 散热基板
11 金属基底
12 导热电绝缘层
13 金属层
20 测试片
21 焊垫
22 测试垫
23 电阻芯片
24 锡膏
具体实施方式
为让本发明的上述和其他技术内容、特征和优点能更明显易懂，下文特举出相关实施例，并配合所附附图，作详细说明如下。
图1为本发明一实施例的散热基板10，包括一金属基底11、一导热电绝缘层12及一金属层13。该导热电绝缘层12设置于该金属基底11上，且该金属层13设置于该导热电绝缘层12上。该金属基底11、导热电绝缘层12及金属层13为层叠结构，或特别是本实施例所示的三明治结构。该导热电绝缘层12包含高分子聚合物以及散布于该高分子聚合物中的导热填料。特别是，本发明选用的导热填料为非圆球形，且该非圆球形导热填料的平均粒径和比表面积的乘积在7.5～15μm·m2/g，因整体导热瑱料的表面积增大，可以利用较少体积百分比的导热填料达到所需的导热率，进而降低导热电绝缘层12的材料硬度，有助于防止锡裂。
以下表1中的实施例1～5为导热电绝缘层12中高分子聚合物的成份，其选用直链型环氧树脂，包含至少两种不同环氧当量(Epoxy Equivalent Weight；EEW)的环氧树脂的混合物。因直链型环氧树脂相较于侧链型环氧树脂较软，故有助于防止锡裂。侧链型环氧树脂有较佳的耐温性，可以少量添加，其于高分子聚合物中的体积占比不超过15vol％或10vol％。实施例1～5中，导热电绝缘层12中高分子聚合物为环氧树脂1、环氧树脂2和环氧树脂3的组合，可以选用其中两种或三种环氧树脂的组合。本实施例中，环氧树脂1选用DowChemical Company的D.E.R.TM331，其EEW为180g/eq。环氧树脂2选用南亚塑胶公司的NPES-904，其EEW为780g/eq。环氧树脂3选用南亚塑胶公司的NPES-619C，其EEW为2700g/eq。本实施例选用不同环氧当量的环氧树脂组合，可调整平均EEW，提供实际特性需求，如Tg、耐温性和耐溶解性等。较大的平均EEW会有较低的Tg和较小的交链密度(crosslink density)。实施例1～5的平均EEW在400～2000g/eq之间，较佳为800～1500g/eq，例如平均EEW可以是500、600、1000、1200、1500或1800g/eq。比较例1和2的平均EEW约2316g/eq，比较例3单纯使用环氧树脂1，其平均EEW为180g/eq。比较例4的平均EEW约1248g/eq，一实施例中，本发明的高分子聚合物包含EEW小于1000g/eq(例如100～400g/eq)的环氧树脂和EEW大于1500g/eq(例如1500～4000g/eq)的环氧树脂，以便于平均EEW的调整。一实施例中，该至少两种不同环氧当量的直链型环氧树脂中至少一种直链型环氧树脂的EEW为100～500g/eq，且占该高分子聚合物的重量百分比大于20％，以获得较佳的耐温性。
表1
参照表2，上述实施例1～5中导热电绝缘层12中的导热填料可包含非圆球形氧化铝，或非圆球形氧化铝和非圆球形氮化铝的混合物。例如表2实施例1～5中的非圆球形氧化铝选用昭和电工型号AL-43M的破碎形氧化铝，其平均粒径为5.54μm，比表面积为1.68m2/g；非圆球形氮化铝选用东洋铝业株式会社(Toyo Aluminium)品名WJB和WM的氮化铝粉混合过筛所得到的破碎形氮化铝，其平均粒径为5.65μm，比表面积为2.14m2/g。其他非圆球形导热填料还可以使用氮化硼和碳化硅等。一实施例中，本发明的非圆球形导热填料的平均粒径为1～30μm，而比表面积为0.2～10m2/g，通常同样材质的导热填料，平均粒径和比表面积的大小呈反向关系。本发明的非圆球形导热填料的平均粒径和比表面积的乘积在7.5～15μm·m2/g之间，或是8、10或12μm·m2/g。因为平均粒径的意义包含尺寸大小和其分布关系，故该乘积与整体导热填料的总表面积成正向关系。导热填料占导热电绝缘层12的体积百分比约在35～65vol％，例如40vol％、50vol％或60vol％。比较例1和4的导热填料选用DENKACo.,Ltd型号DAM-05的球形氧化铝，其平均粒径为5.4μm，比表面积为1.25m2/g(平均粒径和比表面积的乘积约6.75μm·m2/g)，体积百分比约60～70vol％。比较例2和3选用前述破碎形氧化铝，其体积百分比约50vol％。表2中破碎形导热填料的比表面积相较于球形导热填料的比表面积大20％。导热电绝缘层12的其余成份包含上述环氧树脂及相关硬化剂和促进剂等。以上实施例和比较例中的硬化剂使用潜变型硬化剂，例如由Ajinomoto公司生产的AJICURETM MY-24。使用潜变型硬化剂可以延长散热基板固化前半成品的保存时间。
表2
表3为前述实施例1～5和比较例1～4中导热电绝缘层材料的导热率、玻璃转移温度Tg、锡裂测试以及高压蒸煮96小时的金属层剥离强度降低率(％)的测试结果。所述金属层即为设置于该导热电绝缘层12上的金属层13，例如铜箔。实施例1～5中导热电绝缘层材料的导热率约在1～6W/m·K，导热电绝缘层材料(高分子聚合物)的玻璃转移温度在40～90℃，也可以是50℃、60℃、70℃或80℃，且实施例1～5的散热基板10全部通过锡裂测试，其电阻量测均为正常。另外，实施例1～5的散热基板10经96小时于2大气压和121℃饱和蒸气的高压蒸煮测试，其金属层剥离(拉力)强度的降低率在30％以内。反观，比较例3和4的锡裂测试中，测得电阻无限大，即表示电气断路，而认为有锡裂发生。比较例3的平均EEW小于400g/eq，甚至小于200g/eq，因此其Tg较高，质地较脆，容易发生锡裂。比较例4采用球形氧化铝，为了高导热率，使用的体积百分比高达67vol％，导致材料较脆而易锡裂。比较例1和2的锡裂测试的电阻正常，但在经96小时的高压蒸煮测试下，金属层剥离强度的降低率超过40％或50％。比较例1和2的EEW都超过2000g/eq，因此会有较低的Tg和较小的交链密度，使得高压蒸煮测试的金属层剥离强度的降低率过大。显然比较例1～4没有办法同时达到没有锡裂和高压蒸煮金属层剥离强度的降低率小于30％，而本发明的实施例1～5都可以通过锡裂测试，且同时其高压蒸煮测试金属层剥离强度降低率可小于30％。
表3
上述的锡裂测试是先制作长宽2.5cm×1.5cm的测试片20，该测试片20为如同散热基板包含金属基底、导热电绝缘层和金属层的层叠结构。之后将表面金属层蚀刻出图案，其俯视图如图2所示。金属层蚀刻后包含焊垫21和测试垫22，其间有导线连接。之后将电阻芯片23两端利用锡膏24焊接于两侧的焊垫21，如图3的侧面示意图。为简化附图，图3并未绘出测试垫22和其相关连接线路。电阻芯片23焊接于测试片20后，利用两个测试垫22进行电阻量测。电阻芯片23选用YAGEO公司型号PYU-RC0805，芯片尺寸2.0mm×1.2mm，电阻规格330±5％kΩ。锡膏则采用TAMURA公司型号TLF-204-171A的焊锡产品。之后将包含电阻芯片23的测试片20放入冷热循环箱于-40℃维持7分钟之后升温至125℃也维持7分钟形成一循环(cycle)，后续降温至-40℃重启循环。经过2000次循环后，再次量测其电阻。如果经过2000次循环后量测到电阻无限大，即认为锡膏24中有锡裂产生。
表4中实施例6～9和比较例5和6的高分子聚合物都是使用平均环氧当量1248的环氧树脂，添加量均为100重量份。导热填料使用破碎形氧化铝，其占导热电绝缘层中的体积百分比为50％。实施例6～7硬化剂使用AJICURETM MY-24，添加量是3.5重量份。实施例8硬化剂使用AJICURETM PN-50，添加量也是3.5重量份。MY-24和PN-50属于胺加成物(amineadduct)潜变型硬化剂。本发明的胺加成物潜变型硬化剂是使用咪唑化合物(imidazolecompound)、含有3级胺基的化合物(tertiary amino group-containing compound)或酰肼化合物(hydrazide compound)与环氧化合物(epoxy compound)或异氰酸酯化合物(isocyanate compound)反应而成，例如AJICURETM PN-23、AJICURETMPN-40、AJICURETMPN-50、AJICURETM MY-24、AJICURETM MY-H、FujicureTM FXR-1030、AJICURETM VDH、AJICURETMUDH等。其他可使用的潜变型硬化剂还包含酰肼(hydrazide)、二酰肼(dihydrazide)、二氰胺复合物(Dicy)、己二酸二酰肼(adipic acid dihydrazide)以及间苯二甲酸二酰肼(isophthalic dihydrazide)等种类的潜变型硬化剂。实施例9硬化剂使用AJICURETM AH-154，属于二氰胺复合物(Dicy)的潜变型硬化剂，添加量是1重量份。比较例5的硬化剂使用Huntsman公司的D-400，添加量是9.2重量份。比较例6的硬化剂使用Lindau公司的甲基六氢邻苯二甲酸酐(MHHPA)，添加量是12重量份。D-400和MHHPA属于非潜变型硬化剂。实施例6～9和比较例5和6的导热率都是2W/m·K。因硬化剂不同，实施例6～9的Tg约在60℃至85℃之间，而比较例5和6分别为约20℃和95℃，其中显示胺加成物潜变型硬化剂相较于二氰胺复合物(Dicy)潜变型硬化剂，可以得到较低的Tg，而更适于本发明的应用。散热基板的金属层选用一般的铜箔或金属层包含一镀层，该镀层材料可以为锌、铬、镍或其组合，且镀层部分接触该导热电绝缘层。具有镀层的金属层例如是实施例7、8和实施例9的镀镍铜箔，该镀镍铜箔中镀镍部分接触该导热电绝缘层。同样进行前述的锡裂测试及高压蒸煮测试。实施例6～9都没有锡裂问题，且其高压蒸煮金属层剥离强度降低率小于30％，其中使用镀镍铜箔的实施例7、8和9有更好的高压蒸煮金属层剥离强度降低率，可以小于15％，或进一步小于10％。比较例5虽然没有锡裂，但高压蒸煮金属层剥离强度降低率高达58％。比较例6则有锡裂问题。另外，因为MY-24、PN-50和AH-154属于潜变型硬化剂，其有效使用期(pot life)可达90天或120天，然而比较例5和6的有效使用期只有不到1天或约24天。该有效使用期是导热电绝缘层材料在30℃下，其粘度增加为2倍的时间(增加1倍)。依此结果可知实施例6～9的散热基板在30℃环境下经过3个月(90天)后其粘度增加都不会超过1倍。
表4
本发明的导热电绝缘层中的高分子聚合物选用至少两种不同环氧当量的环氧树脂，并搭配潜变型硬化剂，将该高分子聚合物的玻璃转换温度控制在较低温的40～90℃，可有效避免散热基板固定连接芯片的焊锡有时会因在高低温环境中使用而膨胀收缩进而产生锡裂的问题。直链型环氧树脂相较于侧链型环氧树脂较软，不似其较脆硬，故也有助于防止锡裂。此外，本发明特别选用的非圆球形导热填料的平均粒径和比表面积的乘积在在在7.5～15μm·m2/g，因为整体导热填料的表面积增大，可以减少导热填料的使用比例而降低材料的硬度，因而有助于防止锡裂发生。
本发明的技术内容及技术特点已公开如上，然而本领域具有通常知识的技术人士仍可能基于本发明的教示及公开而作种种不背离本发明精神的替换及修饰。因此，本发明的保护范围应不限于实施例所公开的技术内容，而应包括各种不背离本发明的替换及修饰，并为以下的权利要求书所涵盖。

Claims (15)

1.一种散热基板，包括：
一金属基底；
一导热电绝缘层，设置于该金属基底上，该导热电绝缘层包含高分子聚合物以及散布于该高分子聚合物中的非圆球形导热填料，该高分子聚合物包含至少两种不同环氧当量的直链型环氧树脂，该非圆球形导热填料的平均粒径和比表面积的乘积在7.5～15μm·m2/g，该导热电绝缘层的玻璃转换温度在40～90℃，该导热电绝缘层的导热率在1～6W/m·K；以及
一金属层，设置于该导热电绝缘层上；
其中该金属基底、导热电绝缘层及金属层为层叠结构。
2.根据权利要求1所述的散热基板，其中该非圆球形导热填料占该导热电绝缘层的体积百分比35～65％。
3.根据权利要求1所述的散热基板，其中该非圆球形导热填料是选自氧化铝、氮化铝、氮化硼、碳化硅或其组合。
4.根据权利要求1所述的散热基板，其中该非圆球形导热填料包含破碎形导热填料。
5.根据权利要求1所述的散热基板，其中该至少两种不同环氧当量的直链型环氧树脂的平均环氧当量为400～2000g/eq。
6.根据权利要求1所述的散热基板，其中该至少两种不同环氧当量的直链型环氧树脂的平均环氧当量为800～1500g/eq。
7.根据权利要求1所述的散热基板，其中该至少两种不同环氧当量的直链型环氧树脂中的一种直链型环氧树脂的环氧当量为100～400g/eq，另一种直链型环氧树脂的环氧当量为1500～4000g/eq。
8.根据权利要求1所述的散热基板，其中该至少两种不同环氧当量的直链型环氧树脂中至少一种直链型环氧树脂的EEW为100～500g/eq，且占该高分子聚合物的重量百分比大于20％。
9.根据权利要求1所述的散热基板，其中该金属层包含一镀层，该镀层材料可以为锌、铬、镍或其组合，且镀层部分接触该导热电绝缘层。
10.根据权利要求1所述的散热基板，其中该金属层包含镀镍铜箔，且镀镍部分接触该导热电绝缘层。
11.根据权利要求10所述的散热基板，其中该散热基板经高压蒸煮2atm121℃饱和蒸气96小时处理，金属层的剥离强度降低率在30％之内。
12.根据权利要求1所述的散热基板，其中该导热电绝缘层还包含潜变型硬化剂。
13.根据权利要求12所述的散热基板，其中该潜变型硬化剂包含胺加成物、酰肼、二酰肼、二氰胺复合物、己二酸二酰肼以及间苯二甲酸二酰肼中至少一成分。
14.根据权利要求13所述的散热基板，其中该胺加成物是使用咪唑化合物、含有3级胺基的化合物或酰肼化合物与环氧化合物或异氰酸酯化合物反应而成。
15.根据权利要求12所述的散热基板，其中该散热基板在30℃环境下经过3个月后其粘度增加不超过1倍。
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