CN100345472C - 一种热界面材料及其制造方法 - Google Patents
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Abstract
一种热界面材料,其包括一高分子材料以及分布于该高分子材料中的多个碳纳米管,该热界面材料形成有一第一表面及相对于第一表面的第二表面,该碳纳米管两端开口,在该高分子材料中均匀分布且沿热界面材料的第一表面向第二表面延伸并分别伸出两表面形成两弯曲。本发明还提供此种热界面材料的制造方法,包括以下步骤:提供一碳纳米管阵列;将碳纳米管阵列浸润于熔融态高分子;固化该熔融态高分子,生成分布有碳纳米管的高分子复合材料;按照预定厚度切割上述高分子复合材料,形成热界面材料。
Description
【技术领域】
本发明涉及一种热界面材料及其制造方法,尤其涉及一种利用碳纳米管导热的热界面材料及其制造方法。
【背景技术】
近年来,随着半导体器件集成工艺的快速发展,半导体器件的集成化程度越来越高,而器件体积却变得越来越小,其散热成为一个越来越重要的问题,其对散热的要求也越来越高。为了满足这些需要,各种散热方式被大量的运用,如利用风扇散热、水冷辅助散热和热管散热等方式,并取得一定的散热效果,但由于散热器与半导体集成器件的接触界面并不平整,一般相互接触的只有不到2%面积,没有理想的接触界面,,从根本上极大地影响了半导体器件向散热器进行热传递的效果,因此在散热器与半导体器件的接触界面间增加一导热系数较高的热界面材料来增加界面的接触程度就显得十分必要。
传统的热界面材料是将一些导热系数较高的颗粒分散到聚合物材料中形成复合材料,如石墨、氮化硼、氧化硅、氧化铝、银或其它金属等。此种材料的导热性能在很大程度上取决于聚合物载体的性质。其中以油脂、相变材料为载体的复合材料因其使用时为液态而能与热源表面浸润故接触热阻较小,而以硅胶和橡胶为载体的复合材料的接触热阻就比较大。这些材料的一个普遍缺陷是整个材料的导热系数比较小,典型值在1W/mK,这已经越来越不能适应半导体集成化程度的提高对散热的需求,而增加聚合物载体中导热颗粒的含量使颗粒与颗粒尽量相互接触可以增加整个复合材料的导热系数,如某些特殊的界面材料因此可达到4-8W/mK,但当聚合物载体中导热颗粒的含量增加到一定程度时,会使聚合物失去所需的性能,如油脂会***,从而浸润效果会变差,橡胶也会***,从而失去柔韧性,这都会使热界面材料性能大大降低。
近来有一种新的热界面材料,是将定向排列的导热系数约为1100W/mK的碳纤维一端或整个用聚合物固定在一起,从而在聚合物薄膜的垂直方向上形成定向排列的碳纤维阵列,这样每根碳纤维就可以形成一个导热通道,极大提高了这种聚合物薄膜的导热系数,可达到50-90W/mK。但这类材料的一个缺点是不能做得很薄,厚度必须在40微米以上,而材料的热阻与薄膜的厚度成正比,所以,它的热阻降低到一定的程度就难以再进一步降低。
为改善热界面材料的性能,提高其热传导系数,各种材料被广泛的试验。Savas Berber等人于2000年在美国物理学会上发表的一篇名为“UnusuallyHigh Thermal Conductivity of Carbon Nanotubes”的文章指出“Z”形(10,10)碳纳米管在室温下导热系数可达6600W/mK,具体内容可参阅文献Phys.Rev.Lett,vol.84,p.4613。研究如何将碳纳米管用于热界面材料并充分发挥其优良的导热性成为提高热界面材料性能的一个重要方向。
美国专利第6,407,922号揭示一种利用碳纳米管导热特性的热界面材料,其是将碳纳米管掺到基体材料中结成一体,然后通过模压方式制成热界面材料,该热界面材料的两导热表面的面积不相等,其中与散热器接触的导热表面的面积大于与热源接触的导热表面的面积,这样可有利于散热器散热,但该方法制成的热界面材料尚有以下不足,其一,模压方式制成热界面材料较难把厚度做薄,因而,一方面导致该热界面材料导热系数的降低,另一方面,增加该热界面材料的体积,不利于器件向小型化方向发展的需要,且使得热界面材料缺乏柔韧性;其二,该方法制成的热界面材料,碳纳米管杂乱无序的排列在基体材料中,其在基体材料中分布的均匀性较难得到保证,因而热传导的均匀性也受到影响,而且没有充分利用碳纳米管纵向导热的优势,影响了热界面材料的热传导系数。
因此,提供一种厚度薄、导热系数大,接触热阻小,柔韧性好,导热均匀的热界面材料十分必要。
【发明内容】
为解决现有技术的技术问题,本发明的目的是提供一种厚度薄、导热系数大,接触热阻小,柔韧性好,导热均匀的热界面材料。
本发明的另一目的是提供此种热界面材料的制造方法。
为实现本发明的目的,本发明提供一种热界面材料,其包括一高分子材料以及分布于该高分子材料中的多个碳纳米管,该热界面材料形成有一第一表面及相对于第一表面的第二表面,该碳纳米管两端开口,在该高分子材料中均匀分布且沿热界面材料的第一表面向第二表面延伸并分别伸出两表面形成两弯曲。
其中,在该热界面材料中,该碳纳米管基本相互平行且垂直于热界面材料的第一表面和第二表面,该碳纳米管末端的弯曲部分基本平行于热界面材料的第一表面和第二表面。
为实现本发明的另一目的,本发明还提供此种热界面材料的制造方法,其包括以下步骤:
提供一碳纳米管阵列;
将碳纳米管阵列浸润于液相高分子体系;
使液相高分子体系转化为固相,生成分布有碳纳米管的高分子复合材料;
在碳纳米管阵列预定高度,并沿垂直碳纳米管阵列的轴向方向切割该高分子复合材料,去除碳纳米管阵列顶端的高分子材料并使得碳纳米管尖端开口;
按照预定厚度切割上述高分子复合材料,形成热界面材料。
与现有技术相比较,本发明基于碳纳米管阵列导热的热界面材料具以下优点:其一,利用碳纳米管阵列制得的热界面材料,因碳纳米管阵列具有均匀、超顺、定向排列的优点,该热界面材料的每一根碳纳米管均在垂直热界面材料方向形成导热通道,使得碳纳米管的纵向导热特性得到最大限度的利用,因而可得到导热系数高且导热一致均匀的热界面材料;其二,利用本方法制得的热界面材料,不受碳纳米管阵列的生长高度的限制,可通过切割的方法制得厚度极薄的热界面材料,一方面增加了热界面材料的导热效果,另一方面,增加了热界面材料的柔韧性,降低了热界面材料的体积及重量,利于整个器件安装向小型化方向发展的需要;其三,本发明分布在热界面材料中的碳纳米管皆两端开口,且贯穿整个热界面材料并露出两末端,该两末端形成有弯曲基本平行于热界面材料的表面,在应用时,该碳纳米管末端的弯曲部分能增大热界面材料与热源或散热装置的直接接触面积,有利于更好的发挥碳纳米管的导热特性。
【附图说明】
图1是本发明中形成有催化剂薄膜的基底的示意图。
图2是图1所示基底上生长有定向排列的碳纳米管阵列的示意图。
图3是图2所示的碳纳米管阵列连同基底在高分子溶液中浸泡的示意图。
图4是本发明中浸有高分子溶液的碳纳米管阵列的固化的示意图。
图5是本发明中含碳纳米管阵列的热界面材料示意图。
图6是本发明热界面材料的应用示意图。
【具体实施方式】
下面将结合附图及具体实施例对本发明进行详细说明。
请参阅图1和图2,首先在一基底11上均匀形成一层催化剂薄膜12,该催化剂薄膜12的形成可利用热沉积、电子束沉积或溅射法来完成。基底11的材料可用玻璃、石英、硅或氧化铝。本实施例采用多孔硅,其表面有一层多孔层,孔的直径极小,一般小于3纳米。催化剂薄膜12的材料选用铁,也可选用其它材料,如氮化镓、钴、镍及其合金材料等。
然后,氧化催化剂薄膜12,形成催化剂颗粒(图未示),再将分布有催化剂颗粒的基底11放入反应炉中(图未示),在700~1000摄氏度下,通入碳源气,生长出碳纳米管阵列,其中碳源气可为乙炔、乙烯等气体,碳纳米管阵列的高度可通过控制生长时间来控制。有关碳纳米管阵列22生长的方法已较为成熟,具体可参阅文献Science,1999,vol.283,p.512-414和文献J.Am.Chem.Soc,2001,vol.123,p.11502-11503,此外美国专利第6,350,488号也公开了一种生长大面积碳纳米管阵列的方法。
请参阅图3,将熔融态高分子32装进一容器30中,将已生长好的定向排列的碳纳米管阵列22连同基底11一起浸到该熔融态高分子32中,直至熔融态高分子32完全浸润碳纳米管阵列22,熔融态高分子32完全浸润的时间同碳纳米管阵列22的高度、密度以及整个碳纳米管阵列22的面积相关。为使熔融态高分子32能完全浸润碳纳米管阵列22,该熔融态高分子32的粘度在200cPs以下。本发明熔融态高分子32还可用高分子溶液或聚合物单体溶液替代,本实施例采用的熔融态高分子32为熔融态石蜡材料。
请参阅图4和图5,将被熔融态高分子32完全浸润的碳纳米管阵列22连同基底11一起从容器30中取出,冷却使该熔融态高分子32固化,形成高分子材料34。然后在碳纳米管阵列22预定高度,用切片机(图未示)将该高分子材料34沿垂直于碳纳米管阵列22的轴向方向进行切割,形成热界面材料40,其中,在切割前还可进一步将固化后的高分子材料34从基底11上揭下再进行切割,形成热界面材料40。
本发明的热界面材料40的制造方法中也可以先冷却固化该熔融态高分子32,再将固化后形成的高分子材料34连同基底11一起从容器30中取出,然后直接用切片机在碳纳米管阵列22的轴向方向切割该高分子材料34形成热界面材料40。
本发明用切片机切割高分子材料34形成热界面材料40的具体方法为:首先根据碳纳米管阵列22的生长高度将分布有碳纳米管阵列22的高分子材料34沿垂直于碳纳米管阵列22的轴向方向进行切割,除去碳纳米管阵列22上方多余的高分子材料34,同时使碳纳米管的尖端开口;然后按照热界面材料40的所需厚度沿同一方向进行切割,即得到所需的热界面材料40。该热界面材料40中的碳纳米管两端开口,且贯穿整个热界面材料40并露出两末端24,该两末端24分别形成有一弯曲,该弯曲部分基本平行于热界面材料40的表面。在应用时,该碳纳米管末端24的弯曲部分能避免碳纳米管与热源或散热装置的接触不良,增大直接接触面积,从而更好的发挥碳纳米管优良的导热性能。本发明热界面材料40的厚度可为1~1000微米,本实施例热界面材料40的厚度为20微米,由于使用切片机进行切割,热界面材料40的厚度可根据需求由切片时直接控制,方法简单,且容易控制。另外,根据切片机切割方向的不同,碳纳米管末端24可形成有不同方向的弯曲,但大部分都将基本平行于热界面材料40的表面。
本发明的热界面材料40,碳纳米管阵列22经高分子材料34固结形成一体,使得碳纳米管阵列22在高分子材料34中具有分布均匀、垂直排列的特点,在垂直薄膜方向形成导热通道,所形成的热界面材料40具有导热系数高、导热均匀的特点。
利用本方法制得的热界面材料40中,分布在热界面材料40中的碳纳米管阵列22的形态基本未变,即碳纳米管阵列22的中碳纳米管的间距未变,且碳纳米管阵列22没有聚集成束,保持了原有的定向排列的状态,并且此热界面材料40具有良好柔韧性。
另外,由于碳纳米管的两末端24均延伸出热界面材料40并形成有一弯曲平行于热界面材料40的表面,其在应用时能有效的增加碳纳米管与热源或散热装置的接触面积,更好的发挥碳纳米管的优良导热性能。
请参阅图6,本发明制得的碳纳米管阵列热界面材料40具有极佳的导热性能,可广泛的应用于包括中央处理器(CPU)、功率晶体管、视频图形阵列芯片(VGA)、射频芯片在内的电子器件80中,热界面材料40置于电子器件80与散热器60之间,能提供电子器件80与散热器60之间一优良热接触,热界面材料40的第一表面42与电子器件80的表面(未标示)接触,与第一表面42相对应的热界面材料40的第二表面44与散热器60的底面(未标示)接触。由于本发明制得的碳纳米管阵列热界面材料40极薄,其厚度仅在微米级,具有较好的柔韧性,因而,即使在电子器件的表面参差不齐的情况下,本发明的热界面材料也能提供电子器件80与散热器60之间一良好的热接触。另外,由于本发明热界面材料40中的碳纳米管皆两端开口,在且沿热界面材料的第一表面42向第二表面44延伸并分别伸出该两表面42,44形成两弯曲基本平行于热界面材料40的第一表面42和第二表面44。因而,能更好得保证碳纳米管与电子器件80及散热器60的直接接触,使得碳纳米管的纵向导热特性得到最大限度的利用,热界面材料40具有导热系数高且导热一致均匀的特点。
Claims (11)
1.一种热界面材料,其包括一高分子材料以及分布于该高分子材料中的多个碳纳米管,该热界面材料形成有一第一表面及相对于第一表面的第二表面,其特征在于:该碳纳米管两端开口,在该高分子材料中均匀分布且沿热界面材料的第一表面向第二表面延伸并分别伸出两表面形成两弯曲。
2.如权利要求1所述的热界面材料,其特征在于高分子材料中的碳纳米管基本相互平行且垂直于热界面材料的第一表面和第二表面。
3.如权利要求1所述的热界面材料,其特征在于该碳纳米管末端的弯曲部分基本平行于热界面材料的第一表面和第二表面。
4.如权利要求1所述的热界面材料,其特征在于该高分子材料为石蜡。
5.如权利要求1所述的热界面材料,其特征在于该热界面材料的厚度为1~1000微米。
6.一种热界面材料的制造方法,其包括以下步骤:
提供一碳纳米管阵列;
将碳纳米管阵列浸润于液相高分子体系;
使液相高分子体系转化为固相,生成分布有碳纳米管的高分子复合材料;
在碳纳米管阵列预定高度,并沿垂直于碳纳米管阵列轴向切割该高分子复合材料,去除碳纳米管阵列顶端的高分子材料,使得碳纳米管一末端尖端开口并伸出高分子材料形成一弯曲;以及
按照预定厚度并沿垂直于碳纳米管阵列轴向切割上述高分子复合材料,使得碳纳米管另一末端尖端开口并伸出高分子材料形成另一弯曲,形成热界面材料。
7.如权利要求6所述的热界面材料的制造方法,其特征在于液相高分子体系粘度在200cPs以下。
8.如权利要求6所述的热界面材料的制造方法,其特征在于该液相高分子体系包括熔融态高分子、高分子溶液和聚合物单体溶液。
9.如权利要求8所述的热界面材料的制造方法,其特征在于该熔融态高分子包括熔融态石蜡材料。
10.如权利要求6所述的热界面材料的制造方法,其特征在于该碳纳米管阵列生长在一基底上。
11.如权利要求10所述的热界面材料的制造方法,其特征在于切割该高分子复合材料以前进一步包括先将该分布有碳纳米管的高分子复合材料从基底上揭下。
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