CN1275297C - 低介电常数绝缘膜形成用材料、低介电常数绝缘膜、低介电常数绝缘膜的形成方法及半导体器件 - Google Patents
低介电常数绝缘膜形成用材料、低介电常数绝缘膜、低介电常数绝缘膜的形成方法及半导体器件 Download PDFInfo
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- CN1275297C CN1275297C CNB031286232A CN03128623A CN1275297C CN 1275297 C CN1275297 C CN 1275297C CN B031286232 A CNB031286232 A CN B031286232A CN 03128623 A CN03128623 A CN 03128623A CN 1275297 C CN1275297 C CN 1275297C
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Abstract
本发明涉及低介电常数绝缘膜形成用材料、低介电常数绝缘膜、低介电常数绝缘膜的形成方法及具有低介电常数绝缘膜的半导体器件。本发明目的在于提高由多孔膜构成的低介电常数绝缘膜的机械强度。形成低介电常数绝缘膜的溶液含有硅树脂(2)和主要由硅原子及氧原子构成的具有多个空穴的微粒子(3)及溶剂(4)。
Description
技术领域
本发明涉及低介电常数绝缘膜形成用材料、低介电常数绝缘膜、低介电常数绝缘膜的形成方法及具有低介电常数绝缘膜的半导体器件。
背景技术
近年来,为实现半导体器件的微细化、运转高速化和低耗能运转,需要具有低介电常数绝缘膜的多层布线结构。
以往,作为多层布线结构的绝缘膜,采用比介电常数4.2左右的氧化硅薄膜、或比介电常数3.7左右的掺杂氟的氧化硅薄膜等。此外,近来还在研究掺杂甲基(CHF3)的含有有机的氧化硅薄膜,以进一步降低比介电常数。
但是,采用含有有机的氧化硅薄膜,由于很难将比介电常数降低到2.5以下,需要在膜内部导入空穴的绝缘膜,即多孔膜。
以下,就多孔膜的以往技术进行说明。
首先,说明特开2001-294815公报中公开的第1以往例及第2以往例。
第1以往例是通过焙烧由含硅树脂及有机溶剂的溶液形成的薄膜而形成多孔膜的例子。如采用此方法,可在薄膜焙烧时有机溶剂气化消失后留下的痕迹上无规则地形成互连孔。
在此种情况下,有机溶剂起到作为溶剂的作用和帮助形成空穴的作用。此外,一般采用旋涂法在基板上涂布溶液形成薄膜,采用加热板及冶金炉(电炉)焙烧薄膜。
此外,第2以往例是通过焙烧由溶液形成的薄膜而形成多孔膜的例子,上述溶液中除硅树脂及有机溶剂外,通过添加由有机物构成的多孔骨架材料(Porogen)。如采用此方法,通过选择多孔骨架材料,不仅能形成互连孔,而且还可形成独立的孔。此时,多孔骨架材料当然要从薄膜中气化消失。
下面,说明特开平8-181133号公报中提到的第2以往例。
第3以往例是理论上最一般地构成,采用了如图9所示的溶液。即,如图9所示,在容器101中装有混合硅树脂102、多孔骨架材料103及溶剂104的溶液。
特开平8-181133号公报中公开了第3以往例,第3以往例是通过焙烧由含有C60、C70等富勒烯、硅树脂及有机溶剂的溶液形成的薄膜而形成多孔膜的例子。此种情况下富勒烯内部的空心成为空穴。
此外,作为第1、第2及第3以往例中的硅树脂,可采用与无机硅树脂相比,能够低介电常数化的甲基倍半硅氧烷(Methyl-silsesquioxane)那样的有机硅树脂。
以下,参照图10说明一例由以往的溶液形成薄膜的方法。对于利用旋涂法在基板上形成了薄膜的基板,一般可采用加热板或电炉进行焙烧。
首先,如图10(a)所示,在与旋转装置连接的主轴111的上面安装半导体晶片112,然后,通过药液输送管113在该半导体晶片112上面适量滴下溶液114,形成多孔膜。
然后,如图10(b)所示,通过旋转主轴111,转动半导体晶片112,扩展溶液114,形成薄膜115。
然后,如图10(c)所示,通过将形成薄膜115的半导体晶片112放置在加热板116上面,然后加热使溶剂挥发。此工序一般称作预焙,在100℃前后的温度下处理大约1~3分钟。
然后,如图10(d)所示,通过将半导体晶片112放置在加热板117上面,在200℃前后的温度下热处理大约3分钟。此工序一般称作软焙。
然后,如图10(e)所示,将半导体晶片112放置到电炉118中,然后,将电炉的温度升高到约400℃~450℃后,在最高设定温度热处理约1小时。此工序一般称作硬焙,该工序一结束,就在半导体晶片112上形成多孔膜115A。此外,也可利用加热板进行硬焙。另外,根据溶液,优选在软焙和硬焙之间,利用加热板在两者的中间温度下进行约1~3分钟的热处理。
图10(f)是图10(e)中的一段虚线部分的放大图。如图10(f)所示,在半导体晶片112上形成的多孔膜115A的内部形成空穴119(图中用白色表示的部分)。
但是,纳米级压痕评价的上述多孔膜115A的机械强度最大只能得到约5GPa左右的杨氏模量。目前,实际用于半导体器件的有业绩的绝缘膜的模量,以氧化硅薄膜计约为78GPa,以添加氟的氧化硅薄膜计约为63GPa,以含有有机的氧化硅薄膜计约为10GPa。这样,由于多孔膜115A的机械强度比目前正在用于半导体器件的多层布线用绝缘膜的机械强度低,希望开发机械强度高的多孔膜。
图11示出了具有3层布线结构的、同时在使用以往的多孔膜作为绝缘膜的半导体器件上进行丝键合时的截面结构。在图11中,120是半导体晶片,122、124、126是金属布线,123、125、126、128是中空塞,129是用于连接外部布线的垫片。
如图11所示,如在垫片129的上面键合丝130,在垫片129及多层布线部产生断裂。
因此,在层压形成多层布线时,为保持多层布线需要多孔膜115A的机械强度,同时在键合及封装安装上述半导体器件的芯片时也需要多孔膜115A的机械强度。在使用含有有机的氧化硅薄膜作为绝缘膜时,采用目前的键合技术,破坏界限达到极限,今后即使提高键合技术也急需开发高机械强度的多孔膜。
在第1以往例及第2以往例中,由于无规则形成互连孔,为实现比介电常数k=2.2~2.3的低介电常数薄膜,纳米级压痕评价最大只能得到约低于5GPa下的杨氏模量。上述机械强度的提高依赖于有关第1以往例及第2以往例的膜形成方法,即在焙烧的多孔膜中,由于不存在多孔骨架材料及溶剂,只存在硅树脂,多孔膜的机械强度依赖于硅树脂的原有强度和空穴率(单位体积的空穴占有比例)。在第1以往例或第2以往例中,如要使比介电常数降得更低,由于增大空穴率,机械强度会进一步降低。
在第3以往例中,在焙烧后,在多孔膜中还残存富勒烯,但由于其机械强度基本依赖于含有富勒烯的硅树脂的强度,只得到与第1以往例或第2以往例同样的机械强度。此外,富勒烯的含有量如超过30wt%,由于富勒烯相互拴系在一起,机械强度进一步降低。
如上所述,如采用以往的多孔膜的形成方法不能形成适合实用的强固的薄膜,其原因在于硅树脂构成的多孔膜的结构本身的机械强度存在界限。
此外,采用以往的多孔膜,只能达到比半导体器件所需的机械强度小得多的机械强度,如要使多孔膜低介电常数化,存在降低机械强度的问题。
其结果出现的问题是,在将以往的多孔膜实际用于半导体器件的多层布线时,不能制造具有足够强度的半导体器件。此外,即使能够制造半导体芯片,由于在需要封装的安装中损坏半导体器件,不能得到成品。
发明内容
针对上述问题,本发明的目的是提高由多孔膜构成的低介电常数绝缘膜的机械强度。
为达到上述目的,本发明的第1低介电常数绝缘膜形成用材料由含有微粒子、树脂及溶剂的溶液组成,上述微粒子主要由硅原子及氧原子构成并具有多个空穴。
如果采用第1低介电常数绝缘膜形成用材料,确实能够容易形成具有低比介电常数和优良机械强度的低介电常数绝缘膜。
在第1低介电常数绝缘膜形成用材料中,微粒子的尺寸优选大约在1nm以上、30nm以下。
这样,在金属布线相互之间可设置得到的低介电常数绝缘膜的情况下,在金属布线为埋入布线时能够在低介电常数绝缘膜上形成具有良好截面形状的布线槽,在金属布线为图形化的布线时,可形成无空隙的光滑的绝缘膜。
在第1低介电常数绝缘膜形成用材料中,微粒子的空穴的尺寸优选大约在0.5nm以上、3nm以下。
这样,确实能够在微粒子内部形成多个空穴。
在第1低介电常数绝缘膜形成用材料中,微粒子的多个空穴可以相互连接,也可以相互独立。
在第1低介电常数绝缘膜形成用材料中,优选通过机械断裂具有多个无规则分布的互连孔的物质而形成微粒子。
这样就能确实得到具有多个相互连接的空穴的微粒子。
在第1低介电常数绝缘膜形成用材料中,优选通过机械断裂具有多个大约均匀分散的独立孔的物质而形成微粒子。
这样就能确实得到具有多个相互独立的空穴的微粒子。
在第1低介电常数绝缘膜形成用材料中,优选通过化学反应合成微粒子。
这样就能确实得到具有均匀尺寸的微粒子。
在第1低介电常数绝缘膜形成用材料中,树脂优选是硅树脂。
在此种情况下,硅树脂优选含有有机硅。
这样既能够提高所得低介电常数绝缘膜的机械强度,同时又能够降低比介电常数。
在第1低介电常数绝缘膜形成用材料中,树脂优选是有机聚合物。
这样就能够进一步降低所得低介电常数绝缘膜的比介电常数。
在第1低介电常数绝缘膜形成用材料中,优选溶液进一步含有强化树脂与微粒子之间结合的化合物。
这样就能够进一步提高所得低介电常数绝缘膜的机械强度。
本发明的第2低介电常数绝缘膜形成用材料由具有多个由互连孔构成的空穴的微粒子组成,上述微粒子是通过机械断裂主要由硅原子及氧原子构成的并具有多个无规则分布的互连孔的物质而形成的。
如果采用第2低介电常数绝缘膜形成用材料,能够形成具有低比介电常数和优良机械强度的低介电常数绝缘膜。这样,在半导体器件的制造工艺中,像形成多孔膜时一样,由于不受温度、压力或制造气氛体等条件的限制,制造具有无规则分布的互连孔的物质的自由度增大,能够得到高机械强度的微粒子。
本发明的第3低介电常数绝缘膜形成用材料由具有多个由独立孔构成的空穴的微粒子组成,上述微粒子是通过机械断裂主要由硅原子及氧原子构成的并具有多个大约均匀分散的独立孔的物质而形成的。
如果采用第3低介电常数绝缘膜形成用材料,能够形成具有低比介电常数和优良机械强度的低介电常数绝缘膜。这样,在半导体器件的制造工艺中,像形成多孔膜时一样,由于不受温度、压力或制造气氛体等条件的限制,制造具有多个大约均匀分散的独立孔的物质的自由度增大,能够得到高机械强度的微粒子。
本发明的第4低介电常数绝缘膜形成用材料,通过化学合成,主要由硅原子及氧原子构成的具有多个空穴的微粒子构成。
如果采用第4低介电常数绝缘膜形成用材料,能够形成具有低比介电常数和机械强度优良的低介电常数绝缘膜。这样,在半导体器件的制造工艺中,像形成多孔膜时一样,由于不受温度、压力或制造气氛体等条件的限制,制造具有多个空穴的物质的自由度增大,能够得到高机械强度的微粒子。
本发明的低介电常数绝缘膜的形成方法包括:具有在基板上涂布含有微粒子、树脂、溶剂的溶液形成薄膜的工序,上述微粒子主要由硅原子及氧原子构成,具有多个空穴;通过加热上述基板使上述溶剂挥发,形成由上述薄膜构成的低介电常数绝缘膜的工序。
如果采用本发明的低介电常数绝缘膜的形成方法,通过加热基板,使溶剂从由含有微粒子、树脂及溶剂的溶液构成的薄膜上挥发,形成低介电常数绝缘膜。这样,由于在由树脂构成的结构体的内部具有导入含有多个空穴的微粒子的结构,低介电常数绝缘膜就具有低的比介电常数,同时能够提高机械强度。此外,通过增加溶液中的微粒子的比例,可在不降低机械强度的情况下降低比介电常数。
在本发明的低介电常数绝缘膜的形成方法中,微粒子的尺寸优选大约在1nm以上、30nm以下。
这样,在金属布线相互间可设置本发明的低介电常数绝缘膜的情况下,在金属布线为埋入布线时能够在低介电常数绝缘膜上形成具有良好截面形状的布线槽,在金属布线为图形化的布线时可形成无空隙的光滑的绝缘膜。
在本发明的低介电常数绝缘膜的形成方法中,微粒子的空穴的尺寸优选大约在0.5nm以上、3nm以下。
这样就能在微粒子的内部确实形成多个空穴。
在本发明的低介电常数绝缘膜的形成方法中,树脂优选是硅树脂。
这样就能够进一步提高低介电常数绝缘膜的机械强度。
在此种情况下,硅树脂优选含有有机硅。
这样就能够提高低介电常数绝缘膜的机械强度,同时降低比介电常数。
在本发明的低介电常数绝缘膜的形成方法中,树脂优选为有机聚合物。
这样就能够进一步降低低介电常数绝缘膜的比介电常数。
在本发明的低介电常数绝缘膜的形成方法中,溶液优选进一步含有强化树脂与微粒子之间结合的化合物。
这样就能够进一步提高低介电常数绝缘膜的机械强度。
在本发明的低介电常数绝缘膜的形成方法中,加热基板的工序优选包括使树脂与微粒子结合的工序。
这样就能够进一步提高低介电常数绝缘膜的机械强度。
本发明的低介电常数绝缘膜是通过将主要由硅原子及氧原子构成的并具有多个空穴的微粒子与树脂结合而形成。
如果采用本发明的低介电常数绝缘膜,由于具有树脂与具有多个空穴的微粒子相结合的结构,可具有低的比介电常数,同时还能提高机械强度。
在本发明的低介电常数绝缘膜中,微粒子的尺寸优选大约在1nm以上、30nm以下。
这样,在金属布线之间可设置本发明的低介电常数绝缘膜的情况下,在金属布线为埋入布线时能够在低介电常数绝缘膜上形成具有良好截面形状的布线槽,在金属布线为图形化的布线时可形成无空隙的光滑的绝缘膜。
在本发明的低介电常数绝缘膜中,微粒子的空穴的尺寸优选大约在0.5nm以上、3nm以下。
这样,确实能够在微粒子内部形成多个空穴。
在本发明的低介电常数绝缘膜中,树脂优选是硅树脂。
这样就能够进一步提高低介电常数绝缘膜的机械强度。
此种情况下,硅树脂优选含有有机硅。
这样就能够提高低介电常数绝缘膜的机械强度,同时降低比介电常数。
在本发明的低介电常数绝缘膜中,树脂优选为有机聚合物。
这样就能够进一步降低低介电常数绝缘膜的比介电常数。
本发明的低介电常数绝缘膜优选进一步含有强化树脂与微粒子之间结合的化合物。
这样就能够进一步提高低介电常数绝缘膜的机械强度。
本发明的半导体器件具有多根金属布线及在多根金属布线之间形成的低介电常数绝缘膜,低介电常数绝缘膜是通过将主要由硅原子及氧原子构成的并具有多个空穴的微粒子与树脂结合而形成。此外,此处所述的多根金属布线可以是下层的金属布线和上层的金属布线,也可以是在同一布线层相邻的金属布线。
如果采用本发明的半导体器件,由于即使降低低介电常数绝缘膜的比介电常数机械强度也高,能够防止金属布线断裂。
在本发明的半导体器件中,微粒子的尺寸优选大约在1nm以上、30nm以下。
这样,在金属布线为埋入布线时能够在低介电常数绝缘膜上形成具有良好截面形状的布线槽,在金属布线为图形化的布线时可形成无空隙的光滑的绝缘膜。
在本发明的半导体器件中,微粒子的空穴的尺寸优选大约在0.5nm以上、3nm以下。
这样,确实能够在微粒子内部形成多个空穴。
在本发明的半导体器件中,树脂优选是硅树脂。
这样能够进一步提高低介电常数绝缘膜的机械强度。
在此种情况下,硅树脂优选含有有机硅。
这样能够提高低介电常数绝缘膜的机械强度,同时降低比介电常数。
在本发明的半导体器件中,树脂优选是有机聚合物。
这样能够进一步降低低介电常数绝缘膜的比介电常数。
在本发明的半导体器件中,低介电常数绝缘膜优选进一步含有强化树脂与微粒子之间结合的化合物。
这样能够进一步提高所得低介电常数绝缘膜的机械强度。
附图说明
图1是表示第1实施方式的低介电常数绝缘膜形成用材料即溶液的截面图。
图2(a)及(b)是表示第2实施方式的低介电常数绝缘膜形成用材料即微粒子的截面图。
图3(a)及(b)是表示第3实施方式的低介电常数绝缘膜形成用材料即微粒子的截面图。
图4(a)~(c)是表示第4实施方式的低介电常数绝缘膜形成用材料即微粒子的截面图。
图5(a)~(e)是表示第5实施方式的低介电常数绝缘膜形成方法的各工序的截面图。
图6(a)及(b)是第6实施方式的低介电常数绝缘膜的截面图。
图7(a)及(b)是第6实施方式的低介电常数绝缘膜的截面图。
图8是表示第7实施方式的半导体器件的截面图。
图9是表示以往多孔膜形成用溶液的概念图。
图10(a)~(f)是表示以往多孔膜形成方法的各工序的截面图。
图11是说明采用以往多孔膜的半导体器件所存在问题的截面图。图中:1容器,2硅树脂,3具有空穴的微粒子,4溶剂,5多孔结构体,6微粒子,7多孔结构体,8微粒子,9a微粒子,10A第1微粒子,10B第2微粒子,10C第3微粒子,10a有机聚合物,10b有机聚合物,11主轴,12半导体器件,13药液输送管,14溶液,15薄膜,15A低介电常数绝缘膜,16加热板,17加热板,18电炉,20半导体晶片,21低介电常数绝缘膜,22由硅树脂构成的结构体,23微粒子,24由硅树脂构成的结构体,30半导体晶片。
具体实施方式
第1实施方式
以下,参照图1说明本发明的第1实施方式。第1实施方式为由溶液构成的低介电常数绝缘膜形成用材料。
如图1所示,第1实施方式的溶液,装在容器1的内部,含有作为树脂的硅脂2、具有多个空穴的微粒子3和溶剂4。
作为硅树脂2,可以采用无机硅或有机硅或其混合物,如采用有机硅,可以进一步降低所得低介电常数绝缘膜的比介电常数。
作为具有多个空穴的微粒子3,由以硅原子和氧原子的结合为主体的化合物构成,多个空穴可以相互连接,也可以相互独立。
首先,说明相互连接的具有多个空穴的微粒子3的形成方法。
例如,可以通过粉碎具有规则性的中多孔二氧化硅或沸石结晶形成像蜂窝状结构那样的微粒子3。此外,将在形成按第1及第2以往例说明的多孔膜或多孔物质结构体时的焙烧温度(加热板温度)升高到高于第1及第2以往例,在获得强化了硅树脂之间相互结合(交联)的多孔膜或多孔结构体后,可以通过粉碎该多孔膜或多孔结构体形成微粒子3。此外,也可以采用通过四甲氧基硅烷或四乙氧基硅烷等烷氧基硅烷的水解作用生成的胶态硅石、特别是球状胶态硅石作为微粒子3。
下面,说明具有多个相互独立空穴的微粒子3的形成方法。
例如,可以通过粉碎以有机聚合物构成的微粒子作为多孔骨架材料而形成的多孔膜或多孔物质结构体,形成微粒子3。在这种情况下,也可以将在形成按第1及第2以往例说明的多孔膜或多孔物质结构体时的焙烧温度升高到高于第1及第2以往例的焙烧温度,在得到强化了硅树脂之间相互结合的多孔膜或多孔结构体后,通过粉碎该多孔膜或多孔结构体形成微粒子3。此外,也可以采用,以有机聚合物为核心,在该有机聚合物的周围附着胶态硅石特别是球状胶态硅石的此种结构的微粒子3。
此外,无论在何种情况下,作为微粒子3的尺寸,优选大约在1nm以上、30nm以下。作为微粒子3的多个空穴的尺寸,优选大约在0.5nm以上、3nm以下。
作为溶剂4,可以采用在预焙及软焙温度下大约完全蒸发的溶剂,如甲醇、乙醇或异丙醇等醇类,或环己酮、NMP(N-甲基吡咯烷酮)、PGMEA(丙二醇单甲基醚醋酸酯)、PGME(丙二醇单甲基醚)或PGMPE(丙二醇单丙基醚)等有机溶剂。
第2实施方式
以下,参照图2(a)及(b)说明本发明的第2实施方式。第2实施方式为由微粒子构成的低介电常数绝缘膜形成用材料。
图2(a)示出了为形成微粒子6的多孔结构体,图2(b)示出了通过粉碎多孔结构体5得到的微粒子6。
多孔结构体5具有多个无规则分布的互连孔,如果机械断裂该多孔结构体5,可得到具有多个空穴的微粒子6。作为机械断裂多孔结构体5的方法,有通过使多孔结构体5冲撞高速旋转叶片粉碎多孔结构体5的方法及使装在密封容器内部的多孔结构体5冲撞密封容器壁面的断裂方法。如果采用上述方法形成微粒子6,由于可得到各种尺寸的微粒子,优选通过筛选使微粒子6的尺寸大约在1nm以上、30nm以下。
可是,作为多孔结构体5,可以采用像蜂窝状结构一样具有规则性的中多孔二氧化硅或沸石晶体。此外,也可以采用,在形成按第1及第2以往例说明的多孔膜或多孔物质结构体时的焙烧温度(加热板温度)高于第1及第2以往例的焙烧温度下,经过焙烧强化了硅树脂之间相互结合(交联)的多孔膜或多孔结构体。
微粒子6的空穴的尺寸优选大约在0.5nm以上、3nm以下。
第3实施方式
以下,参照图3(a)及(b)说明本发明的第3实施方式。第3实施方式为由微粒子8构成的低介电常数绝缘膜形成用材料。
图3(a)示出了为形成微粒子8的多孔结构体7,图3(b)示出了通过粉碎多孔结构体7得到的微粒子8。
多孔结构体7具有多个大约均匀分散的独立孔,如果机械断裂该多孔结构体7,可得到具有多个空穴的微粒子8。作为机械断裂多孔结构体7的方法,有通过使多孔结构体7冲撞高速旋转叶片的粉碎方法及使装在密封容器内部的多孔结构体7冲撞密封容器壁面的断裂方法。采用上述方法形成微粒子8,由于可得到各种尺寸的微粒子,优选通过筛选使微粒子8的尺寸大约在1nm以上、30nm以下。
可是,作为多孔结构体7,可以采用以由有机聚合物构成的微粒子作为多孔骨架材料而形成的多孔膜或多孔物质结构体。在此情况下,如在比第1及第2以往例中的焙烧温度高的温度下进行焙烧,可得到机械强度优良的多孔结构体7。此外,微粒子8的空穴的尺寸优选大约在0.5nm以上、3nm以下。
第4实施方式
以下,参照图4(a)~(c)说明本发明的第4实施方式。第4实施方式为由通过化学反应合成的微粒子构成的低介电常数绝缘膜形成材料。
图4(a)示出了通过化学反应合成的具有多个空穴的第1微粒子10A,该第1微粒子10A由微粒子9a构成,微粒子9a是由通过四甲氧基硅烷或四乙氧基硅烷等烷氧基硅烷的水解作用生成的胶态硅石、特别是球状胶态硅石构成的,并具有多个空穴。此外,也可以采用中多孔二氧化硅或沸石晶体的微粒子代替胶态硅石,作为微粒子9a。
图4(b)表示通过化学反应合成的具有多个空穴的第2微粒子10B,该第2微粒子10B具有的结构为:具有多个空穴的微粒子9a大约均匀附着在具有相对较小外径的有机聚合物10a的周围。作为微粒子9a,可以采用通过四甲氧硅烷或四乙氧基硅烷等烷氧基硅烷的水解作用生成的胶态硅石。此外,也可以采用中多孔二氧化硅或沸石晶体的微粒子代替胶态硅石作为微粒子9a。此外,作为微粒子9a及有机聚合物10a的形状,可以是球状的,也可以是多面体状的。
图4(c)表示通过化学反应合成的具有多个空穴的第3微粒子10C,该第3微粒子10C具有的结构为:具有多个空穴的微粒子9a大约均匀附着在具有相对较大外径的有机聚合物10b的周围。作为微粒子9a,可以采用通过四甲氧硅烷或四乙氧基硅烷等烷氧基硅烷的水解作用生成的胶态硅石。此外,也可以采用中多孔二氧化硅或沸石晶体的微粒子代替胶态硅石作为微粒子9a。此外,作为微粒子9a及有机聚合物10b的形状,可以是球状的,也可以是多面体状的。另外,作为在有机聚合物10b的周围附着微粒子9a的配置方法,优选采用可提高第3微粒子10C机械强度的不大均匀的特殊配置。
此外,关于第1、第2或第3微粒子10A、10B、10C的尺寸,优选大约在1nm以上、30nm以下;关于微粒子9a的空穴的尺寸,优选大约在0.5nm以上、3nm以下。
第5实施方式
以下,参照图5(a)~(e)说明本发明的第5实施方式。第5实施方式是采用有关第1实施方式的溶液的低介电常数绝缘膜及其形成方法。
首先,如图5(a)所示,准备有关第1实施方式的溶液。即,在容器1的内部装入按第2~第4实施方式说明的硅树脂2、微粒子3及溶剂4。接着在与旋转装置连接的主轴11的上面安装半导体晶片12,然后,通过与容器1连接的药液输送管13在该半导体晶片12上适量滴下溶液14。
然后,如图5(b)所示,通过旋转主轴11转动半导体晶片12,使溶液14扩展形成薄膜15。
然后,如图5(c)所示,将形成薄膜15的半导体晶片放置在加热板16上,通过加热挥发溶剂。该工序一般称作预焙,在100℃左右的温度下热处理1~3分钟。
然后,如图5(d)所示,将半导体晶片12放置在加热板17上,在200℃左右的温度下热处理1~3分钟。该工序一般称作软焙。
然后,如图5(e)所示,将半导体晶片12放入电炉18中后,将温度升高到大约400℃~450℃,然后,在设定的最高温度下热处理1小时。该工序一般称作硬焙。该工序一结束,就在半导体晶片12形成由硅树脂2和微粒子3组成的低介电常数绝缘膜15。此外,也可以利用加热板进行硬焙。另外,在软焙和硬焙之间,优选利用加热板在两者的中间温度下进行约1~3分钟的热处理。
如采用第5实施方式,硅树脂2在软焙工序中,大概形成基本的硅氧烷结构,结构上大约稳定化,在其后进行的硬焙工序中硅氧烷骨架相互形成交联,形成强固而且机械强度优良的低介电常数绝缘膜15A。即,在软焙工序中,硅树脂2之间相互结合,同时具有空穴的微粒子3也与硅树脂结合。
这样,如采用第5实施方式,低介电常数绝缘膜15A由于具有硅树脂2与具有空穴的微粒子3强固结合的结构,与只由硅树脂构成的硅氧烷结构体相比,能形成强韧性、高机械强度的多孔膜。
第6实施方式
以下,参照图6(a)、(b)及图7(a)、(b)说明本发明的第6实施方式。第6实施方式也是采用有关第1实施方式的溶液的低介电常数绝缘膜及其制造方法。
可是,如果采用有关第5实施方式的方法形成低介电常数绝缘膜,在低介电常数绝缘膜的内部形成的空穴的样式根据溶剂的分子结构变化。即,(1)在采用在预焙中大约能完全蒸发掉的像乙醇一样的溶剂时,除了微粒子内部存在的多个空穴外,几乎不形成空穴。然而,(2)无论采用在预焙完全不蒸发、在软焙大约完全蒸发的溶剂还是采用由具有直链状或接近直链状的结构的分子构成的溶剂时,除微粒子内部存在的多个微粒子外,在有硅树脂构成的部分都容易形成连接的孔。这样,不同的溶剂种类在低介电常数绝缘膜中所形成的空穴的形状也不同。以下参照图6(a)、(b)说明此点。
图6(a)表示在半导体晶片20上面形成的第1低介电常数绝缘膜21的截面结构,该第1低介电常数绝缘膜21由具有空穴的硅树脂21和具有多个空穴的微粒子23构成。此外,在硅树脂21的内部白色表示的部分为空穴。在第1低介电常数绝缘膜21中,通过具有在微粒子23中存在的多个空穴和在硅树脂21的内部形成的互连孔可形成整体具有互连孔的多孔膜。
图6(b)表示在半导体晶片20上形成的第2低介电常数绝缘膜24的截面结构,该第2低介电常数绝缘膜24由具有空穴的硅树脂22和具有多个空穴的微粒子23构成。在第2低介电常数绝缘膜24中,由于硅树脂24不具有空穴,可形成整体相互独立的具有多个空穴的多孔膜。
图7(a)示出了图6(a)所示的第1低介电常数绝缘膜21的第1样式,该第1样式是采用溶质中微粒子23所占比例低于30wt%~50wt%的低介电常数形成材料而形成。在第1样式中,由硅树脂22构成的结构体超过半数,该结构体中存在具有空穴的微粒子23,硅树脂22构成的结构体和具有微粒子23强固结合。如第1样式一样,在硅树脂22构成的结构体的内部,如掺入机械强度比硅树脂22高的微粒子23,能够得到机械强度比只由硅树脂22构成的结构体高得多的薄膜。
图7(b)示出了图6(a)所示的第1低介电常数绝缘膜21的第2样式,该第2样式是采用溶质中微粒子23所占比例低于30wt%~50wt%的低介电常数形成材料而形成。在第2样式中,具有空穴的微粒子23构成第1低介电常数绝缘膜21的主骨架,相邻的微粒子23之间相互结合以连接硅树脂22构成的结构体。如采用第2样式,由于在硅树脂22构成的结构体的内部掺入机械强度比硅树脂22高的微粒子23,能够得到机械强度比只由硅树脂22构成的结构体高得多的薄膜,同时与第1样式相比,由于具有空穴的微粒子23的比例增大,可进一步降低比介电常数。
如上所述,如采用有关第5或第6实施方式的低介电常数绝缘膜,由于在硅树脂构成的结构体的内部掺入具有多个空穴的微粒子,能够得到比介电常数一般低于2.5的同时机械强度高的多孔膜。有关第5或第6实施方式的低介电常数绝缘膜的机械强度,以杨氏模量计一般在6GPa以上。
即,如采用有关第5或第6实施方式的低介电常数绝缘膜,为在薄膜中形成空穴而掺入的具有多个空穴的微粒子在成膜过程中不消失,残存在多孔膜中,同时与由硅树脂构成的结构体牢固结合。因此,如果具有空穴的微粒子在溶液中的比例提高到30wt%以上,必然能增大低介电常数绝缘膜中的空穴率,同时进一步降低比介电常数,与采用富勒烯时一样,不但不降低机械强度而且还能得到增大的效果。
此外,作为硅树脂,如采用硅与有机基如甲基结合的有机硅,或采用含有有机硅的硅树脂,能够进一步降低低介电常数绝缘膜的比介电常数。
此外,如采用由芳基·醚结合或芳基·芳基结合构成的聚合物等有机聚合物代替硅树脂,能够进一步降低低介电常数绝缘膜的比介电常数。这是因为相对于大部分MSQ的比介电常数一般在2.9,大部分上述有机聚合物的比介电常数小于2.6。因此,由于硅树脂及有机聚合物成立与具有空穴的多孔薄模时相同的关系,所以通过用有机聚合物代替硅树脂易于促进低介电常数化。
此外,在采用图7(a)示出的第1低介电常数绝缘膜21的第1样式时,如在溶液中添加强化硅树脂与微粒子结合的化合物,能够进一步提高机械强度。
此外,在采用图7(b)示出的第1低介电常数绝缘膜21的第2样式时,如在溶液中添加强化含硅树脂的微粒子相互之间结合力的化合物,能够进一步提高机械强度
此外,作为强化硅树脂与微粒子结合的化合物,可以采用烷氧基硅烷。例如,由于二甲基二甲氧基硅烷在硅中与2个甲基(CH3-)和2个甲氧基(CH3O-)结合,能够在成膜时的软焙及硬焙中促进硅树脂和微粒子的连接。此外,烷氧基硅烷由于也能够促进微粒子之间的连接和有机聚合物与微粒子的连接,适合作为强化本发明的结合力的化合物。
第7实施方式
以下,参照图8说明本发明的第7实施方式。第7实施方式为具有低介电常数绝缘膜的半导体器件。
图8表示在半导体器件上进行丝键合时的截面结构,该半导体器件具有多层布线结构例如3层布线结构,同时作为绝缘膜还具有有关第5或第6实施方式的低介电常数绝缘膜。在图11中,30是半导体晶片,31是低介电常数绝缘膜,32、34、36是金属线,33、35、36、38是中空塞,39是连接外部布线的垫片。作为构成金属布线32、34、36的金属布线材料可以是铜或铝合金。此外,在采用铜布线时,可用铜作中空塞,在采用铝布线时,可用钨作中空塞。
如图8所示,可通过在垫片39上面键合丝40封装组装(未图示)半导体器件。
如采用第7实施方式,由于低介电常数绝缘膜31与以往的多孔膜相比机械强度高,在垫片39及金属布线32、34、36不产生断裂。此外,由于低介电常数绝缘膜31保持金属布线32、34、36的强度也大,能够得到稳定的半导体器件。
如采用本发明的第1~第4的低介电常数绝缘膜形成用材料,确实能够容易形成具有低比介电常数同时又具有优良机械强度的低介电常数绝缘膜。
如采用本发明的低介电常数绝缘膜及其形成方法,确实能够容易形成具有低比介电常数同时又具有优良机械强度的低介电常数绝缘膜。此外,通过提高溶液中的微粒子的比例,能够在不降低机械强度的条件下降低比介电常数。
如采用本发明的半导体器件,由于能够降低低介电常数绝缘膜的比介电常数同时提高机械强度,能够防止金属布线发生断裂。
Claims (32)
1.一种低介电常数绝缘膜形成用材料,其特征在于:由含有微粒子、树脂和溶剂的溶液构成,所述微粒子主要由硅原子及氧原子构成,具有空穴,所述空穴的尺寸在0.5nm以上、3nm以下,所述微粒子的尺寸是1nm以上且30nm以下。
2.如权利要求1所述的低介电常数绝缘膜形成用材料,其特征在于:所述微粒子中所含的空穴相互连接。
3.如权利要求1所述的低介电常数绝缘膜形成用材料,其特征在于:所述微粒子中所含的空穴相互独立。
4.如权利要求1所述的低介电常数绝缘膜形成用材料,其特征在于:所述微粒子是通过机械断裂具有无规则分布的多个相连空穴的物质而形成。
5.如权利要求1所述的低介电常数绝缘膜形成用材料,其特征在于:所述微粒子是通过机械断裂具有大致均匀分散的多个独立空穴的物质而形成。
6.如权利要求1所述的低介电常数绝缘膜形成用材料,其特征在于:通过化学反应合成所述微粒子。
7.如权利要求1所述的低介电常数绝缘膜形成用材料,其特征在于:所述树脂为硅树脂或有机聚合物。
8.如权利要求7所述的低介电常数绝缘膜形成用材料,其特征在于:所述硅树脂含有在硅原子与甲基之间形成化学键的有机硅。
9.如权利要求1所述的低介电常数绝缘膜形成用材料,其特征在于:所述溶液进一步含有强化所述树脂与所述微粒子之间结合的化合物。
10.根据权利要求1所述的低介电常数绝缘膜形成用材料,其特征在于:所述微粒子主要由多孔二氧化硅或沸石晶体构成。
11.根据权利要求7所述的低介电常数绝缘膜形成用材料,其特征在于:所述有机聚合物具有芳基·醚结合或芳基·芳基结合。
12.根据权利要求1所述的低介电常数绝缘膜形成用材料,其特征在于:所述微粒子在所述溶剂中含有30wt%以上。
13.一种低介电常数绝缘膜的形成方法,其特征在于:具有在基板上涂布含有微粒子、树脂、溶剂的溶液形成薄膜的工序,所述微粒子主要由硅原子及氧原子构成,具有空穴;通过加热所述基板挥发所述溶剂,形成由所述薄膜构成的低介电常数绝缘膜的工序,
所述空穴的尺寸在0.5nm以上、3nm以下,所述微粒子的尺寸是1nm以上且30nm以下。
14.如权利要求13所述的低介电常数绝缘膜的形成方法,其特征在于:所述树脂为硅树脂或有机聚合物。
15.如权利要求14所述的低介电常数绝缘膜的形成方法,其特征在于:所述硅树脂含有在硅原子与甲基之间形成化学键的有机硅。
16.如权利要求13所述的低介电常数绝缘膜的形成方法,其特征在于:所述溶液进一步含有强化所述树脂与所述微粒子之间结合的化合物。
17.如权利要求13所述的低介电常数绝缘膜的形成方法,其特征在于:所述低介电常数绝缘膜的形成工序包括所述微粒子与所述树脂的结合工序。
18.根据权利要求13所述的低介电常数绝缘膜的形成方法,其特征在于:所述微粒子主要由多孔二氧化硅或沸石晶体构成。
19.根据权利要求13所述的低介电常数绝缘膜的形成方法,其特征在于:所述微粒子在所述溶剂中含有30wt%以上。
20.一种低介电常数绝缘膜,其特征在于:通过使主要由硅原子及氧原子构成的具有空穴的微粒子与树脂结合而形成,所述空穴的尺寸在0.5nm以上、3nm以下,所述微粒子的尺寸是1nm以上且30nm以下。
21.如权利要求20所述的低介电常数绝缘膜,其特征在于:所述树脂为硅树脂或有机聚合物。
22.如权利要求21所述的低介电常数绝缘膜,其特征在于:所述硅树脂含有在硅原子与甲基之间形成化学键的有机硅。
23.如权利要求20所述的低介电常数绝缘膜,其特征在于:含有进一步强化所述树脂与所述微粒子之间结合的化合物。
24.根据权利要求20所述的低介电常数绝缘膜,其特征在于:所述微粒子主要由多孔二氧化硅或沸石晶体构成。
25.根据权利要求21所述的低介电常数绝缘膜,其特征在于:所述有机聚合物具有芳基·醚结合或芳基·芳基结合。
26.一种半导体器件,其特征在于:具有多条金属布线和在所述多条金属布线之间形成的低介电常数绝缘膜;
所述低介电常数绝缘膜是通过使主要由硅原子及氧原子形成的具有空穴的微粒子与树脂结合而形成,
所述空穴的尺寸在0.5nm以上、3nm以下,所述微粒子的尺寸是1nm以上且30nm以下。
27.如权利要求26所述的半导体器件,其特征在于:所述树脂为硅树脂或有机聚合物。
28.如权利要求27所述的半导体器件,其特征在于:所述硅树脂含有在硅原子与甲基之间形成化学键的有机硅。
29.如权利要求26所述的半导体器件,其特征在于:所述低介电常数绝缘膜进一步含有强化所述树脂与所述微粒子之间结合的化合物。
30.根据权利要求26所述的半导体器件,其特征在于:所述微粒子主要由多孔二氧化硅或沸石晶体构成。
31.根据权利要求26所述的半导体器件,其特征在于:所述多个金属布线之一与垫片连接,所述垫片与金属丝键合。
32.根据权利要求26所述的半导体器件,其特征在于:所述微粒子在所述低介电常数绝缘膜中含有30wt%以上。
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JP2002137893A JP3859540B2 (ja) | 2002-05-14 | 2002-05-14 | 低誘電率絶縁膜形成用材料 |
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CN1461047A CN1461047A (zh) | 2003-12-10 |
CN1275297C true CN1275297C (zh) | 2006-09-13 |
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US (4) | US20030213958A1 (zh) |
JP (1) | JP3859540B2 (zh) |
KR (1) | KR100559562B1 (zh) |
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CN101887853A (zh) * | 2009-05-13 | 2010-11-17 | 尔必达存储器株式会社 | 低k膜的制造方法、半导体装置及其制造方法 |
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JP3859540B2 (ja) * | 2002-05-14 | 2006-12-20 | 松下電器産業株式会社 | 低誘電率絶縁膜形成用材料 |
US7081393B2 (en) * | 2004-05-20 | 2006-07-25 | International Business Machines Corporation | Reduced dielectric constant spacer materials integration for high speed logic gates |
JP4798329B2 (ja) * | 2004-09-03 | 2011-10-19 | Jsr株式会社 | 絶縁膜形成用組成物、絶縁膜、およびその形成方法 |
US7531209B2 (en) * | 2005-02-24 | 2009-05-12 | Michael Raymond Ayers | Porous films and bodies with enhanced mechanical strength |
US7312512B2 (en) * | 2005-09-28 | 2007-12-25 | Taiwan Semiconductor Manufacturing Co., Ltd. | Interconnect structure with polygon cell structures |
US7919188B2 (en) | 2006-05-31 | 2011-04-05 | Roskilde Semiconductor Llc | Linked periodic networks of alternating carbon and inorganic clusters for use as low dielectric constant materials |
WO2007143029A1 (en) * | 2006-05-31 | 2007-12-13 | Roskilde Semiconductor Llc | Porous materials derived from polymer composites |
WO2007143025A2 (en) * | 2006-05-31 | 2007-12-13 | Roskilde Semiconductor Llc | Porous inorganic solids for use as low dielectric constant materials |
WO2007143028A2 (en) | 2006-05-31 | 2007-12-13 | Roskilde Semiconductor Llc | Low dielectric constant materials prepared from soluble fullerene clusters |
JP5098507B2 (ja) | 2007-08-10 | 2012-12-12 | 東京エレクトロン株式会社 | 半導体装置の製造方法、半導体製造装置及び記憶媒体 |
KR102053350B1 (ko) | 2013-06-13 | 2019-12-06 | 삼성전자주식회사 | 저유전율 절연층을 가진 반도체 소자를 형성하는 방법 |
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-
2002
- 2002-05-14 JP JP2002137893A patent/JP3859540B2/ja not_active Expired - Lifetime
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2003
- 2003-04-28 CN CNB031286232A patent/CN1275297C/zh not_active Expired - Fee Related
- 2003-05-14 TW TW092113083A patent/TWI254987B/zh not_active IP Right Cessation
- 2003-05-14 KR KR1020030030428A patent/KR100559562B1/ko not_active IP Right Cessation
- 2003-05-14 US US10/437,299 patent/US20030213958A1/en not_active Abandoned
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101887853A (zh) * | 2009-05-13 | 2010-11-17 | 尔必达存储器株式会社 | 低k膜的制造方法、半导体装置及其制造方法 |
CN101887853B (zh) * | 2009-05-13 | 2014-02-05 | Ps4拉斯口有限责任公司 | 低k膜的制造方法、半导体装置及其制造方法 |
Also Published As
Publication number | Publication date |
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CN1461047A (zh) | 2003-12-10 |
KR100559562B1 (ko) | 2006-03-10 |
JP3859540B2 (ja) | 2006-12-20 |
US20050263908A1 (en) | 2005-12-01 |
KR20030088376A (ko) | 2003-11-19 |
US20030213958A1 (en) | 2003-11-20 |
US20060202356A1 (en) | 2006-09-14 |
TW200400559A (en) | 2004-01-01 |
JP2003327843A (ja) | 2003-11-19 |
US7563706B2 (en) | 2009-07-21 |
TWI254987B (en) | 2006-05-11 |
US20070218643A1 (en) | 2007-09-20 |
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