CN116580872A - 自致密纳米银浆及制备用于高功率电子器件的互连层的方法 - Google Patents

自致密纳米银浆及制备用于高功率电子器件的互连层的方法 Download PDF

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CN116580872A
CN116580872A CN202310063633.6A CN202310063633A CN116580872A CN 116580872 A CN116580872 A CN 116580872A CN 202310063633 A CN202310063633 A CN 202310063633A CN 116580872 A CN116580872 A CN 116580872A
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Prior art keywords
silver
interconnect
particles
nanoparticles
trimodal
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CN202310063633.6A
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王悦辰
徐涛
傅丽
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Nano and Advanced Materials Institute Ltd
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Nano and Advanced Materials Institute Ltd
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Publication of CN116580872A publication Critical patent/CN116580872A/zh
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Abstract

在选自GaN或SiC体系的高温半导体装置与基板之间形成自致密互连层。互连层包括具有微米级银颗粒的基质，其含量约为10至60重量百分比，且该微米级银颗粒具有约0.1至15微米的粒径；键合颗粒以化学键合的方式连接基质中的微米银颗粒，且该键合颗粒包括核心银纳米颗粒，以及以原位形成并且以化学结合的方式结合到核心银纳米颗粒的表面银纳米颗粒，同时该表面银纳米颗粒也以化学结合的方式与具有微米级银颗粒的基质结合。该键合颗粒具有约10至100纳米的核心粒径，而原位形成的表面银纳米颗粒具有约3至9纳米的粒径。

Description

自致密纳米银浆及制备用于高功率电子器件的互连层的方法
相关申请的交叉引用
本申请要求对2022年1月16日提交的美国临时专利申请案63/300,043、及2023年1月12日提交的美国专利申请案18/154,033享有优先权，通过引用将其公开内容并入本文。
技术领域
本发明涉及自致密纳米银浆，更具体地，涉及用于连接高功率电子装置的自致密纳米银浆。
背景技术
由于金属纳米颗粒及其相关油墨/浆剂具有颗粒尺寸减小和表面积增加的独特特性，因此在印刷电子行业引起了广泛的兴趣。近来，已有以喷墨印刷方法直接使用金属纳米颗粒油墨于印刷精细导电图案的方法，这种特殊的方法所用的油墨必须含有高浓度的小纳米颗粒，其可以很好地分散在溶剂中。例如，WO2009/111393公开了一种导电油墨，其包括金属纳米粒子、聚合物分散剂和溶剂，并进一步公开了金属纳米粒子的含量约占油墨的10-60重量百分比。
在半导体封装中，芯片贴装材料可在半导体器件与其基板/封装之间形成电和/或热连接，传统上，常以铅基焊料形成这种连接，因此，用于芯片贴装的高温铅基焊料合金在半导体工业领域中属于成熟产品，然而，铅基材料会引起环境和健康问题。某些地区的环境法规规定，封装需要使用无铅焊料，但无铅焊料合金的熔化温度通常较低，容易受到热疲劳和蠕变的影响，从而产生长期的可靠性问题，虽然金基的无铅焊料合金具有可接受的电和热性能，但在大多数设备中使用过于昂贵。
高功率半导体装置具有较高的击穿电压以及较低的开关损耗，能够实现更高的电流密度，并在更高的温度下运作。这些高功率装置会使用到宽带隙材料，如碳化硅(SiC)和氮化镓(GaN)，这两种材料都可以在300℃以上的温度下运作。由于在高功率电子装置中使用这些宽带隙材料会增加对高散热的需求，共晶焊料合金或常规芯片贴装粘合剂并不适合作为芯片贴装材料，因为其散热能力有限(导热率30-60W/mK)且熔点低。使用这些常规材料的键合线显示出较低的热稳定性，并且在高操作温度下会失效，因此，考虑到键合层材料的低导热性，可能反而需要限制高功率电子装置的功率。
透过银烧结，可以在装置和基板之间提供牢固的键合(bond)。在烧结过程中，当银材料在最佳条件(压力、温度和时间)下加热时，其形态会从粉末变为固体结构；与传统的焊料材料相比，银烧结可产生更可靠的互连层，具有显著提高的性能和寿命，且更节能并对半导体封装产生的应力更小。
由于银纳米粒子具有高熔化温度(961℃)和低烧结温度，银纳米粒子已被大量使用于半导体装置和基板的互连，透过其优异的导热性和导电性，烧结银能够将装置的结温度(junction temperature，Tj)降低至100℃。当颗粒尺寸减小到纳米级时，会产生一些特殊的特性，如较低的熔化温度、较高的表面能和较高的扩散系数，这些特性与块体银明显地不同。
烧结纳米银的优点之一是其可以在与铅基焊料相当的温度下形成连接层(joint)；然而，烧结后，连接层不会熔化，直到温度超过银的熔点(961℃)，且纳米银材料还具有与银块相同的优异热、电和机械性能，在相对较低的温度下所生产的烧结纳米银连接层可以在常规焊点失效的高温(超过500℃)下使用。
大多数的银纳米颗粒的用途涉及热和压力，以实现紧密互连；压力辅助的烧结方法需要投入大量资本投资于压力施加设备，并且具有非常低的制造吞吐量，且过程中的高压也可能导致芯片裂开。
美国专利号8257795涉及一种浆料，其金属颗粒全为纳米颗粒，可在加热过程中选择使用压力，然而，完全由纳米颗粒制成的浆料可能较难进行加工。在一个方面，由于纳米颗粒容易结块，导致浆料堵塞点胶器，并影响最终粘结层的密度，导致可加工性降差；此外，金属纳米颗粒通常比微米范围尺寸颗粒更昂贵，增加了浆料成本和使用浆料的装置的总成本。表1中比较了不同的传统芯片贴装材料的效能。
表1﹕传统芯片贴装材料的效能
因此，本领域需要改进芯片贴装材料，使其可用于在高温半导体装置(例如GaN或SiC基器件)和基板之间形成互连层。
发明内容
本发明提供了高温半导体装置与基板之间的自致密互连层，其中该高温半导体装置选自GaN或SiC体系装置，该互连层包括具有微米级银颗粒的基质，其约占10-60重量百分比，且该微米级银颗粒具有约0.1-15微米的粒径；并使用键合颗粒化学结合微米级银颗粒的基质，该键合颗粒是一种具有原位(in-situ)形成的较小的表面银纳米颗粒的核心银纳米颗粒，该表面银纳米颗粒透过化学结合的方式与核心银纳米颗粒结合，同时也透过化学结合的方式与具有微米级银颗粒的基质结合，且该键合颗粒具有约10至约100纳米的核心粒径，而该原位形成的表面银纳米颗粒具有约3-9纳米的粒径。
在另一方面，该微米级银颗粒是银薄片或近似球形的银颗粒。
在另一方面，该基板包括厚度约为0.1至0.3微米的银或金层。
在另一方面，本发明提供一种三峰(trimodal)的自致密互连银浆，该浆料包括10-60重量百分比的基质银颗粒，其约为微米等级，平均粒径为0.1-15微米，且该浆料还包括10-60重量百分比的键合银纳米颗粒，该键合银纳米颗粒具有尺寸约10-100纳米的核心银纳米颗粒。核心银纳米颗粒具有聚合物包覆层，其包含溶解或悬浮的银盐前驱物，银盐前驱物可形成粘结到核心银纳米颗粒表面的表面银纳米颗粒，且该核心银纳米颗粒具有约10-100纳米的粒径，因此可形成具有3-9nm纳米粒径的表面纳米颗粒的复合银纳米颗粒。该浆料还包括10-20重量百分比的至少一种还原性溶剂和0.1-1重量百分比的抗氧化还原剂。
在另一方面，该浆料可包含30-50重量百分比的基质颗粒、10-30重量百分比的键合颗粒和20-40重量百分比的溶剂。
在另一方面，该浆料可包含20-50重量百分比的基质颗粒、30-40重量百分比的键合颗粒和20-30重量百分比的溶剂。
在另一方面，该浆料可包含30-40重量百分比的基质颗粒、30-40重量百分比的键合颗粒和20-30重量百分比的溶剂。
在另一方面，该浆料可包含20-40重量百分比的基质颗粒、30-50重量百分比的键合颗粒和10-20重量百分比的溶剂。
该三峰的互连银浆还可包含0.1-1重量百分比的非导电填料。
在该三峰的互连银浆中，约微米等级的基质银颗粒可以是银薄片或近似球形的银颗粒。
该三峰的互连银浆的聚合物包覆层可以是聚乙烯吡咯烷酮。
在该三峰的互连银浆中，该银盐可以是硝酸银、氯化银、乙酸银或硫酸银中的一种或多种。
在该三峰的互连银浆中，该至少一种还原性溶剂可以是乙二醇、二甘醇、三甘醇或聚乙二醇中的一种或多种。
在该三峰的互连银浆中，该抗氧化还原剂可以是柠檬酸、咖啡酸、苹果酸或二羧酸中的一种或多种。
在该三峰的互连银浆中，该非导电填料可以是SiC、SiO2、Al2O3、ZrO2、硅树脂微球颗粒或在烧结温度下稳定的其他陶瓷和聚合物颗粒中的一种或多种。
在另一方面，本发明还提供了一种在高温半导体装置和基板之间形成自致密互连键合层的方法，其中高温半导体装置选自GaN或SiC基装置，其包含将该浆料置在该半导体装置和基板之间，并进行多步骤加热，将该三峰的自致密互连银浆加热至约80至120℃之间的第一温度并持续一段足以在核心银纳米颗粒表面上原位形成表面银纳米颗粒的时间。
将浆料加热至约120至150℃之间的第二温度，持续一段足以去除基质银颗粒上的有机层的时间；将浆料加热至约150至200℃之间的第三温度，持续一段足以去除残留溶剂的时间；最后，将浆料加热至约200至260℃之间的第四温度，持续一段足以将互连银浆烧结成互连键合层的时间。
在另一方面，该足以在核心银纳米颗粒表面上原位形成表面银纳米颗粒的时间约为10至30分钟。
在另一方面，该足以去除基质银颗粒上的有机层的时间约为10至30分钟。
在另一方面，该足以烧结互连银浆以形成互连层的时间约为30-90分钟。
在另一方面，该互连键合层是在不给予/添加压力的情况下形成。
附图说明
图1显示根据本发明一实施例的封装半导体装置的示意图；
图2A-2B是应用于图1的封装半导体装置中的互连结构和键合颗粒的放大示意图；
图3显示银的熔化温度与颗粒直径的关系图；
图4显示根据本发明一实施例的的键合；
图5显示在核心银纳米颗粒上形成银纳米颗粒；
图6显示本发明中的固化曲线；以及
图7显示微米级银颗粒与纳米级颗粒的键合。
具体实施方式
概述：
银是一种柔软、延展性很强的金属，具有很高的导电性和导热性，而银纳米粒子，其通常小于100nm，在空气中不氧化，并且在水中稳定，由于银纳米颗粒独特的物理和化学特性，像是光学、电学、热学和生物学特性，近来被应用于越来越多地的领域，包括医疗、食品、保健、消费和工业用途。随着银的尺寸范围转变到纳米级，由于具纳米结构的银具有更高的比表面能和更高的表面体积比，使其对热的敏感性提升。另外，表面扩散系数也会随颗粒尺寸的减小而增加，表示纳米颗粒的比表面能会高于微粒或块状材料的比表面能；且扩散的驱动力与颗粒的大小成反比，高驱动力会导致银纳米颗粒的烧结温度降低。图3中显示了不同尺寸的银颗粒的熔化温度，从图中可见直径小于10nm的颗粒熔化温度的显着降低。
图1示意性地显示采用本发明的互连材料的半导体封装100。半导体封装包括装置10和基板20，装置10可以是GaN基或SiC基装置，而基板20可以是陶瓷材料或能够承受高温的其他材料。该装置通过互连层/芯片贴装层25连接至基板，基板20可以包括上基板金属化层55和下基板金属化层50，该基板20可以通过贴装焊料30贴装到底板40。封装可由填充有可选封装化合物70的可选保护壳60界限，且电源端子65可以穿过保护壳60以建立到电源和其他装置的连接，一个或多个引线键合可以将装置10连接到基板金属化层。
互连/芯片贴装层25具有图2A所显示的微结构的金属层，互连层25包括具有微米等级的银颗粒26的基质，其含量约为10-60重量百分比；其中微米级的银颗粒26的粒度范围约为0.1-15微米；键合颗粒，用于化学结合具有微米级银颗粒26的基质，键合颗粒是具有原位形成的表面银纳米颗粒28(图2B)的核心银纳米颗粒27，该表面银纳米颗粒28化学结合到核心银纳米微粒27的表面，同时也化学结合到具有微米级银颗粒26的基质，键合颗粒具有约10-100纳米的核心银纳米颗粒27，而原位形成的表面银纳米颗粒28具有约3-9纳米的颗粒尺寸。
图2A-2B的互连层25由三峰的自致密金属互连浆制成。术语“三峰(trimodal)”涉及金属互连浆中使用的三种金属颗粒。值得注意的是，术语“墨水/油墨(ink)”和“浆/浆料/浆剂(paste)”在本说明书中有时可互换；通常，浆剂的粘度比油墨高，油墨往往更具流动性。本领域技术人员应可理解这些粘度差异，以及如何从高粘度浆剂(通常通过较大百分比的溶剂)中产生低粘度油墨。在三峰浆剂中，微米等级的基质金属颗粒与键合颗粒可一并使用，该键合颗粒包括具有原位形成的较小的金属颗粒附着于表面的金属纳米颗粒核心，该浆剂包括10-60重量百分比的微米等级基质银颗粒，其平均粒径为0.1-15微米，且该浆剂还包括10-60重量百分比的键合银纳米颗粒，其具约10-100纳米的核心银纳米颗粒，该核心银纳米颗粒具有聚合物包覆层，其包含溶解或悬浮其中的银盐前驱物，该银盐前驱物可形成粘附到核心银纳米颗粒表面的表面银纳米颗粒；其中核心银纳米颗粒具有约10-100纳米的粒径。当生成时，从银盐前驱物分解而来的表面银纳米颗粒具有3-9纳米的粒径，其将结合到约10-100纳米的粒径的核心银纳米颗粒表面。因此，具有高表面能的较小的表面纳米颗粒将比核心纳米颗粒和微米等级的银基质颗粒更快地熔化，可用作结合核心颗粒和基质颗粒的结合剂；该浆剂还包括10-20重量百分比的至少一种还原性溶剂和0.1-1重量百分比的抗氧化还原剂。
本发明浆剂也包括其他組成范围，例如，该浆剂可以包括30-50重量百分比的基质颗粒、10-30重量百分比的键合颗粒和20-40重量百分比的溶剂；或者，该浆剂可以包括20-50重量百分比的基质颗粒、30-40重量百分比的键合颗粒和20-30重量百分比的溶剂；在另一个方面，该浆剂可以包括30-40重量百分比的基质颗粒、30-40重量百分比的键合颗粒和10-30重量百分比溶剂；在另一方面，该浆剂可包括20-40重量百分比的基质颗粒、30-50重量百分比的键合颗粒和10-20重量百分比的溶剂。
在一个方面，互连/芯片贴装层25可用于与下表面上具有薄金属层21的半导体芯片/装置10接合；在一个实施例中，该薄金属层可以是薄银或薄金层；类似地，基板20的上表面上可存有薄金属层21；每个薄金属层具有约0.1-0.3微米的厚度。使用薄金属层可以防止互连/芯片贴装层材料25在接合界面处失效。
材料
微米级银颗粒
在本发明的三峰纳米银浆组合物中，该微米级银颗粒，较优选地可包括银薄片或近似球形的银颗粒的至少一种，其粒径约为0.1-15微米；银片的平均粒径优选为0.1-15μm，因为当粒径小于0.1μm时，键合层结构将具有高孔隙率，并且银层的热导率将相对降低；当粒径超过15μm时，很难从点胶器中挤出银片。微米级银薄片可以在键合结构内以高密度建立导电通路，此外，与使用银球形颗粒的浆剂相比，使用银薄片的浆剂提供了更好的印刷性。
该浆剂较优选地含有约10-60质量百分比的银薄片，当其含量低于10质量百分比时，键合结构显示出高孔隙率，并呈现低导热性和较差的剪切强度性能；如果银薄片含量超过60质量百分比时，则烧结结构也将显示出较差的剪切强度，因为银键合颗粒所形成的银烧结键合数量不足。在另一方面，该浆剂可包含20-50质量百分比的银薄片或30-50质量百分比银薄片，20-40质量％银薄片或30-40质量％银薄片。
键合纳米颗粒
图5分别显示较小的表面纳米颗粒与核心纳米颗粒形成表面结合之前与之后的结合纳米颗粒27。浆剂中的键合核纳米颗粒27为尺寸约10-100纳米的颗粒，其涂覆有聚合物29；在一个方面，聚合物29可含有银盐，如硝酸银、氯化银、乙酸银或硫酸银的聚乙烯吡咯烷酮(PVP)。银纳米颗粒可透过如下所述方式合成：
银纳米颗粒混合物的合成
1.在90-160℃的温度下，以机械搅拌将聚乙烯吡咯烷酮(PVP)溶解在乙二醇(EG)或二甘醇(DEG)中。
2.向上述PVP溶液中添加任选的还原剂，还原剂的选择及其浓度取决于所选择的金属盐。
3.将金属盐溶解在去离子水或乙二醇溶液中。
4.以受控的速度将银盐溶液加入PVP溶液中。
5.反应完成后，通过离心的方式从溶液中分离出银纳米颗粒。
6.透过丙酮/醇溶剂冲洗并通过离心分离，以纯化纳米颗粒。
或者，可以用催化还原改性剂PVP形成银纳米颗粒混合物。PVP作为保护剂，其剂量和分子量可有效的控制银颗粒的形态、分散性和尺寸，PVP的分子量可为10000至100000Mw。当分子量低于10000呈低分子量(Mw)和低玻璃化转变温度(Tg)时，PVP无法有效地控制金属盐，因为纳米银的尺寸分布在还原过程中涵盖更广；并且当Mw大于100000时，PVP很可能形成线状，使纳米银趋向于组装成线状结构。因此，将选择40000的分子量作为PVP的分子量，以良好地控制纳米银的尺寸，如下示意性所示：
银盐和PVP之间的质量比例可选择为1:3至1:7；其也包括1:4至1:6、1:5至1:7和1:4至1:5。
当质量比例低于1:3时，纳米银的平均粒径太大，容易聚集；而超过1:7时，纳米银改性层将太厚，无法被洗掉。
如图5所示，所形成的银纳米颗粒28的平均尺寸为10-100nm。用丙酮/醇溶剂洗涤具有PVP包覆层29的银纳米颗粒28，并通过离心分离几次，用上述步骤合成的PVP包覆层包含用于原位银纳米颗粒形成的Ag离子。
还原性溶剂
可选溶剂可与银颗粒混合物一起使用，该溶剂可以使用任何已知的还原剂溶剂作为溶剂，该溶剂较优选为乙二醇基溶剂，乙二醇基溶剂包括乙二醇、二甘醇、三甘醇和聚乙二醇、丙二醇、二丙二醇等，本发明的三峰纳米银浆组合物可任选地包括至少一种还原性溶剂，其可以是上述溶剂之一或组合，且该还原性溶剂的用量优选为约10-30质量百分比，包括10-20质量百分比和20-30质量百分比。
用作还原剂的溶剂不仅将银离子转化为结合在核心银纳米颗粒表面上的银纳米颗粒，还可去除待结合基板上的任何氧化层，并在键合线层和基板之间或键合线和芯片之间提供了牢固的连接；特别地，还原性溶剂的还原能力在固化过程中随着温度的升高可进一步增加，因此可以在银纳米颗粒成核期间延长固化时间，以获得最大量的在原位形成的银纳米颗粒，且在适当的温度下延长固化时间，亦可进一步从基材上去除任何氧化层；此外，还原溶剂还可去除浆剂中银薄片的任何表面涂层，例如硬脂酸或氧化物，否则，银薄片上的此类涂层将降低键合线层的热导率。因此，固化膜是致密的，并具有高导电性，且对基板和芯片具有高粘附性。
选择还原性溶剂的另一个考虑因素是沸点。由于银浆在高达260℃的温度下烧结时，溶剂的沸点不应超过260℃，且原位银纳米颗粒的形成发生在约80-120℃，应可选择沸点超过120℃的还原性溶剂；因此，溶剂的沸点选择为约120至260℃，更优选为150至260℃。为了进一步延长溶剂留在浆剂中的时间，以确保有足够时间形成原位颗粒和去除氧化层，溶剂可以是两种不同溶剂的组合，且每种溶剂具有不同的沸点，因此，溶剂可以逐步的方式蒸发，这也将有助于产生更紧密的键合结构。
溶剂的量优选为银的10至20质量份，如果小于10质量份，会使粘度增加并且降低其可加工性；如果超过20质量份，会使粘度降低，并导致浆剂太薄而无法印刷。
抗氧化还原剂
可将抗氧化还原剂添加到三峰纳米银浆的组合物中。在本发明中，抗氧化还原剂是指那些具有助焊活性的材料，以用于去除基板与芯片的氧化物涂层、微米级银颗粒表面上的硬脂酸涂层，以及银纳米颗粒上的残余PVP涂层，此外，还可防止基板表面在高温固化期间被再次氧化。干净的基板表面有助于键合界面处的机械强度，避免裂纹形成，且干净的微米级银颗粒表面也有助于提高导热性。抗氧化还原剂包括柠檬酸、咖啡酸、苹果酸和二羧酸(例如乙二酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸等)。若其使用量小于0.1％，则没有还原作用，如果抗氧化还原剂的使用量超过1质量百分比，则会降低键合的导热性；另外，抗氧化还原剂的分解温度不应超过200℃，以便在银的烧结过程开始前，可于150-200℃的温度范围内去除还原剂，因为若未能在烧结前去除还原剂，可能会对粘结产生负面影响，导致剪切强度降低。
可选非导电填料
本发明的三峰纳米银浆组合物可任选地包括非导电填料。非导电填料可选自SiC、SiO2、TiO2、Al2O3中的一种或多种，或在烧结温度下稳定的其他陶瓷和聚合物颗粒，例如硅树脂微球。向浆料中添加非导电填料的目的是使浆料结构致密化，避免颗粒生成过程中出现会对剪切强度和导热性产生负面影响的空隙聚集。非导电颗粒的加入可提高烧结纳米银键合的高温稳定性和高水热稳定性，还可以限制在低温和高温的热循环期间热阻的增加，且剪切强度随三峰纳米银浆中SiC比例的增加而上升。非导电填料颗粒的尺寸优选在约50-1000nm之间。当银浆中具有非导电填料时，其含量相对于100质量份的三峰纳米银浆组分优选为0.1至1质量百分比。
分步固化致密方法
在另一方面，本发明提供了一种多步骤固化方法，该方法可使金属浆自致密，并可在低温下形成牢固的键合，且无需在键合过程中施加压力。该多步骤固化方法包括(S1)原位形成银纳米颗粒，(S2)去除微米级银颗粒的氧化层并结合银纳米颗粒，(S3)去除残余抗氧化还原剂，以及(S4)烧结银纳米颗粒。图6示意性地显示了本发明的多步骤固化方法，因此，三峰纳米银浆的多步骤固化方法在芯片和基板之间提供了致密的键合结构，且无需在键合期间给予外部压力。
第一步中，从包围核心纳米颗粒的聚合物层中的金属盐中原位产生银纳米颗粒，其生成温度约为80～120℃，生成时间约10-30分钟；第二步，从基板和微米级银薄片/球形银颗粒上的有机层上去除氧化层，此步骤的温度约为120～150℃，持续约10-30分钟；第三步，去除残留的抗氧化还原剂，操作温度约为150～200℃，持续时间约为10-30分钟；第四步，烧结银纳米颗粒，烧结温度约为200-260℃之间，持续约30-90分钟。图7中示意性地显示了在溶剂中的颗粒，并在去除溶剂时，颗粒与微米级银颗粒结合。
使用本发明的三峰纳米银浆剂组合物和多步骤固化方法，从含有银盐的聚合物/PVP涂层中形成围绕键合顆粒的核心纳米颗粒的原位银纳米颗粒，如图5所示，在含有同時充当还原剂的乙二醇基溶剂時，在键合纳米颗粒的表面上产生一定量的小尺寸银纳米颗粒(3-9nm)，以在核纳米颗粒(較大)上形成較小的纳米颗粒的壳。重要的是，在烧结成更大的微米级银薄片/球形银颗粒之前，将小的纳米颗粒28與基質银纳米颗粒27化学结合。
可对组合物进行优化，以确保具有高填充密度。由于在多步骤固化和烧结过程中，溶剂材料会缓慢的被去除，因溶剂/添加剂的蒸发/分解所产生的空隙会被银纳米颗粒27填充；也就是说，由于其高堆积密度和多步骤固化方法，该结构是自致密的；由于在步骤2和3中去除溶剂和添加剂时所形成的自致密结构，当在固化/烧结方法的最后步骤中，即烧结三峰纳米银浆时，很少会形成空隙；且原位形成的银纳米颗粒在低温(约112℃)烧结，并作为银纳米颗粒上的金属粘合剂，银纳米颗粒在较大的微米级颗粒中可作为强结合颗粒。上述的三种银颗粒的最终键合结构如图2A所示。
实施例1：具有PVP包覆的银纳米颗粒的合成
36.4g聚乙烯吡咯烷酮(PVP)(Mw为50000)在磁力搅拌下溶解于75mL乙二醇中，并加热至120℃，再将5.8g硝酸银溶解于25mL乙二醇。接着将硝酸银溶液加入PVP溶液中，搅拌反应1小时，然后冷却至室温。反应完成后，以10000rpm离心出混合物，并用乙醇和丙酮洗涤。将未干燥纯化的银纳米颗粒保存在乙醇中，用于随后的油墨/浆剂制备。
实施例2：三峰纳米银浆的配方
下表中列出根据本发明的几种组合物配方以及比较组合物。如下表所示，根据本发明的组合物在热老化前后，表现出具有显著性的更高的导热性和更高的剪切强度。此外，与现有的组合物(比较组合物)相比，本发明的组合物的孔隙率和电阻率较低。
表2：特定配方的范例：
*分步固化轮廓：上述步骤固化致密化方法。
控制固化方式：
·P2：在260℃下直接固化
·P3：在30℃时达到平衡，以10℃/分钟的速度升温至130℃，等温30分钟，以10℃/
分钟的速度升温到260℃，等温60分钟。
工业适用性
透过结合本发明的三峰纳米银浆料与多步骤固化致密化/键合方法，可用于无压烧结，也可用于加压烧结，该键合在半导体装置和基板之间表现出优异的粘合性，该键合还显示出优异的剪切强度，并且在高温老化试验期间具有高导热性和高热稳定性。
如本文所用且未另行定义，术语“实质性”、“实质性地”、“近似的”和“大约的”用于描述和说明微小的变化。当与事件或情况一起使用时，术语可以包括事件或情况精确发生的实例以及事件或情况接近发生的实例。例如，当与数值一起使用时，这些术语可以包含小于或等于该数值的±10％的变化范围，例如小于或等于±5％、小于或等于±4％、小于或等于±3％、小于或等于±2％、小于或等于±1％、小于或等于±0.5％、小于或等于±0.1％或小于或等于±0.05％。
上述描述是为了说明和描述本发明的目的，其并非旨在穷尽或将本发明限制于所公开的精确形式，对于本领域技术人员来说，许多修改和变化将是显而易见的，选择和描述上述实施例是为了最好地解释本发明的原理及其实际应用，从而使本领域的其他技术人员能够理解本发明的各种实施例以及适合于预期的特定用途的各种修改。

Claims (16)

1.一种在选自GaN或SiC体系的高温半导体装置与基板之间形成的自致密互连层，其特征在于，包括：
具有微米级银颗粒的基质，其含量占10-60重量百分比，且所述微米级银颗粒的粒径范围为0.1至15微米；
键合颗粒，所述键合颗粒可与所述具有微米级银颗粒的基质融合，其是一种表面具有原位形成的较小的表面银纳米颗粒的核心银纳米颗粒，其中所述原位形成的表面银纳米颗粒透过化学结合的方式结合于所述核心银纳米颗粒的表面，并也透过化学结合的方式与所述具有微米级银颗粒的基质结合，其中所述键合颗粒具有10至100纳米的核心粒径，而所述原位形成的表面银纳米颗粒具有约3至9纳米的粒径。
2.根据权利要求1所述的自致密互连层，其中所述微米级银颗粒选自银薄片或近似球形的银颗粒。
3.根据权利要求1所述的自致密互连层，其中所述基板包括厚度为0.1至0.3微米的银或金层。
4.一种三峰自致密互连银浆，其特征在于，包括：
10至60重量百分比的平均粒径为0.1至15微米的约微米等级的基质银颗粒；
10至60重量百分比的键合银纳米颗粒，所述键合银纳米颗粒具有约为10至100纳米的核心银纳米颗粒，所述核心银纳米颗粒具有聚合物包覆层，其包含溶解或悬浮的银盐前驱物，所述银盐前驱物可形成粘结到所述核心银纳米颗粒表面的表面银纳米颗粒；
10至20重量百分比的至少一种还原性溶剂；以及
0.1至1重量百分比抗氧化还原剂。
5.根据权利要求4所述的三峰互连银浆，其中所述三峰自致密互连银浆进一步包含0.1-1重量百分比的非导电填料。
6.根据权利要求4所述的三峰互连银浆，其中所述约微米等级的基质银颗粒选自银薄片或近似球形的银颗粒。
7.根据权利要求4所述的三峰互连银浆，其中所述聚合物包覆层是聚乙烯吡咯烷酮。
8.根据权利要求4所述的三峰互连银浆，其中所述银盐前驱物选自硝酸银、氯化银、乙酸银或硫酸银中的一种或多种。
9.根据权利要求4所述的三峰互连银浆，其中所述至少一种还原性溶剂选自乙二醇、二甘醇、三甘醇或聚乙二醇中的一种或多种。
10.根据权利要求4所述的三峰互连银浆，其中所述抗氧化还原剂选自柠檬酸、咖啡酸、苹果酸或二羧酸中的一种或多种。
11.根据权利要求5所述的三峰互连银浆，其中所述非导电填料选自SiC、SiO2或Al2O3、ZrO2、硅树脂微球颗粒或在烧结温度下稳定的其他陶瓷和聚合物颗粒中的一种或多种。
12.一种在选自GaN或SiC体系的高温半导体装置和基板之间形成自致密互连键合层的方法，其特征在于，包括：
将三峰自致密互连银浆置于选自GaN或SiC体系的高温半导体装置和基板之间，其中所述三峰自致密互连银浆包括：
10至60重量百分比的平均粒径为0.1至15微米的约微米等级的基质银颗粒；
10至60重量百分比的键合银纳米颗粒，所述键合银纳米颗粒具有约为10至100纳米的核心银纳米颗粒，所述核心银纳米颗粒具有聚合物包覆层，其包含溶解或悬浮的银盐前驱物，所述银盐前驱物可形成粘结到所述核心银纳米颗粒表面的表面银纳米颗粒；以及
10至20重量百分比的至少一种还原性溶剂；
将所述三峰自致密互连银浆加热至80至120℃之间的第一温度，并持续一段足以在所述核心银纳米颗粒表面上原位形成表面银纳米颗粒的时间；
将所述三峰自致密互连银浆加热至120至150℃之间的第二温度，并持续一段足以去除所述基质银颗粒上的有机层的时间；
将所述三峰自致密互连银浆加热至约150至200℃之间的第三温度，并持续一段足以去除残留溶剂的时间；以及
将所述三峰自致密互连银浆加热至约200至260℃之间的第四温度，并持续一段足以将银互连浆烧结成互连键合的时间。
13.根据权利要求12所述的用于形成互连键合层的方法，其中所述足以在核心银纳米颗粒表面上原位形成表面银纳米颗粒的时间约为10至30分钟。
14.根据权利要求12所述的用于形成互连键合层的方法，其中所述足以去除基质银颗粒上的有机层的时间约为10至30分钟。
15.根据权利要求12所述的用于形成互连键合层的方法，其中所述足以烧结银互连浆以形成互连的时间约为30-90分钟。
16.根据权利要求12所述的用于形成互连键合层的方法，其中所述互连键合是在不给予/添加压力的情况下形成。
CN202310063633.6A 2022-01-16 2023-01-16 自致密纳米银浆及制备用于高功率电子器件的互连层的方法 Pending CN116580872A (zh)

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CN116890110A (zh) * 2023-09-11 2023-10-17 长春永固科技有限公司 一种可低温烧结的微米银粉及制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116890110A (zh) * 2023-09-11 2023-10-17 长春永固科技有限公司 一种可低温烧结的微米银粉及制备方法
CN116890110B (zh) * 2023-09-11 2024-01-02 长春永固科技有限公司 一种可低温烧结的微米银粉及制备方法

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