CN1184272C - 用于化学机械平面加工的含过氧化物抛光液的稳定方法 - Google Patents
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Abstract
本发明的一个实施例是一种电气器件的制造方法。所述电气器件具有一覆盖在半导体基片上的结构,所述基片使用化学机械平面加工方法进行平面加工。所述方法包括下述步骤:在半导体晶片上形成一材料层;将所述晶片置于一抛光垫上,对其材料层进行抛光,所用抛光液含有过氧化物;其中所述抛光液还包括一可阻止抛光液中过氧化物分解的稳定剂。所述稳定剂较好的是:焦磷酸,多磷酸,多膦酸,乙二胺四乙酸,焦磷酸盐,多磷酸盐,多膦酸盐,乙二胺四乙酸盐及由上述化合物之间的任一种混合物。另外,上述稳定剂可以包括:焦磷酸钠的十水合物及/或8-羟基喹啉。抛光液中的过氧化物的分解受到含于抛光液中的过渡金属的催化作用,也可由抛光液中的pH引起。所述的材料层较好的是:钨、铜、铝、电介质材料及其组合材料。
Description
本发明涉及一种半导体装置的制造及加工方法,特别是,本发明涉及一种使化学机械平面加工用的含过氧化物抛光液(slurry)稳定的方法。
当今,半导体装置制造领域中存在的二个倾向,其中之一是希望所述半导体装置具有平面结构,其中另一个是减少覆盖所述半导体基片的结构材料中的杂质。化学—机械抛光(CMP)工艺被越来越频繁地用于上述二个倾向性的制造方法中。大多数半导体制造商使用CMP加工电介质层材料层表面及对某些金属结构进行平面(化)加工。用于所述CMP工艺中最普遍的方法是:将半导体晶片通过一安装垫(mounting pad),固附于一支承座(所述支承座可以是转动或不可转动的)上,并使所述晶片的外露表面与一抛光垫(polishing pad,该抛光垫安装于一旋转或不旋转的台板上)接触,由此对晶片的外露表面进行抛光。在晶片表面和抛光垫之间发生的机械磨擦形成对所述晶片表面的抛光作用。为有助于上述表面抛光并去除在该抛光过程中产生的颗粒,通常的作法是,在所述晶片表面和抛光垫之间加入一种抛光液。所述抛光液的化学组成与晶片表面发生反应,由此,使晶片的抛光更加易于进行。而过剩的抛光液将该抛光过程中产生自所述晶片的物质带走。
如今,大多数用于半导体工业的加工方法通常都要在晶片上形成一层导体材料层或绝缘材料层,随后对上述材料层进行平面加工(典型的是CMP)。例如,通常是先将一层与其它材料比较非常薄的电介质层沉积形成于晶片上。由于晶片表面上的形貌,使得所述电介质层的厚度表现出其量相当显著的差异。并且,由于这些表面层的高度变化,使得在使用现行的平版印刷方法及其设备时,很难制得那些须形成于该材料层之中的、用以形成内部传导布线图案的通路孔/沟槽。因此,人们要求在上述通路孔的布线图案形成之前,先进行平面加工步骤。该步骤典型的是用CMP方法进行,藉由所述方法,将在电介质层表面形成相对较平坦的上表面。
另外,CMP方法可以用于在导体材料(例如,钨、铜、铝、或其它金属/金属组合物)表面覆盖层生成之后,形成如通路孔及/或内部互联沟槽等的嵌入式导电结构。这里,比较、对照CMP与反应性离子蚀刻(“RIE”)方法的不同,可以看到,上述二种方法加工的平面更加清洁,并更加平坦。通常,敷加金属覆盖层的工艺过程如下:首先在一电介质层上开出许多孔,用于形成通孔路及/或内部互联沟槽,然后,在其上面覆盖形成(或有选择地形成)所述导体材料的覆盖层,以填充所述通路孔及/或内部布互联沟槽。为了将所述导体材料恰当地填充于所述孔槽中,较好的是,将一过剩量的导体材料沉积于所述晶片上。然而,这将导致在所述电介质层的孔槽之外的区域也形成导体材料层。为了去除这些过剩的材料,可以使用CMP方法。
在某些敷加金属过程中,可以藉由对所述CMP工艺采用一氧化剂,以增大所述过剩量导体材料(或电介质材料)的去除效率,由此,使得须除去的材料至少被部分氧化。能够提高去除效率的理由是:某些被氧化的材料更加柔软,从而,这些材料更容易比未氧化的材料被去除。再有,上部的氧化避免其内部材料氧化,由此,可以对平面加工进行控制。例如,氧化钨较软,所以,氧化钨更容易从钨金属中被去除。由此,一些半导体装置的制造商在对钨金属进行抛光时,对所述抛光液添加过氧化氢或其它氧化剂,使得部分钨金属(通常是钨金属结构的顶层)氧化,由此,使得这些部分容易被去除。所述过氧化物可在将抛光液使用于抛光须去除材料层之前添加于该抛光液中,或者,所述过氧化物可另外添加于所述抛光垫上。然而,较好的是,在将抛光液供至CMP工具之前,将过氧化氢以约为1-10的重量百分比混合于抛光液中,这样,使得抛光工艺的控制和操作更加简单。请见John P.Bare & Budge Johl著,“用于钨的含氧化氢基CMP抛光液的制造及操作性能的评价”,IEEE/CPMTINTERNATIONAL ELECTRONIC MANUFACTURING TECHNOLOGY SYMPOSIUM 164171(1998)。然而,该方法存在一个问题是,过氧化氢抛光液的储存寿命较短。工业上通常可以见到:含有过氧化氢的抛光液在静止状态时,以约为0.1%(重量)/天的速率分解。这即意味着,所述抛光液随着时间流逝,其有效性递减。图1的曲线102表明过氧化氢在一典型的商业可购的钨抛光液中的分解情况。此时,过氧化氢分解的结果是,使用该抛光液时CMP加工方法时,材料的去除率是完全不可预见的。最后,该去除率变得如此低,使得所述抛光液无法再利用,而必须废弃。
上述分解现象可用若干不同的理论解释。本领域的许多技术人员认为,照射至抛光液的UV辐射,升高的温度,及某些抛光液的高pH等是控制过氧化氢分解于所述抛光液中的主要原因。然而,本发明的发明者发现:抛光液中存在的过渡金属可能是促使过氧化氢在抛光液中分解的主要因素。抛光液中存在的过渡金属会对过氧化氢的分解反应起快速的催化作用,由此,形成水和氧这些产物。
本发明的一个实施例是制造一种电气器件的制造方法。所述电气器件具有一覆盖在半导体基片上的结构,所述基片使用化学机械平面加工(抛光)方法进行平面加工。所述方法包括下述步骤:
在半导体晶片上形成一材料层;
将所述晶片置于一抛光垫上,用抛光液对其材料层进行抛光,所用抛光液含有过氧化物;
所述抛光液还包括一可阻止抛光液中过氧化物分解的稳定剂。
所述稳定剂较好的是选自:焦磷酸,多磷酸,多膦酸,乙二胺四乙酸,焦磷酸盐,多磷酸盐,多膦酸盐,乙二胺四乙酸盐及由上述化合物组成的任一种混合物。另外,上述稳定剂可以包括:焦磷酸钠的十水合物及/或8-羟基喹啉。抛光液中的过氧化物的分解可因含于抛光液中的过渡金属而被催化,也可能由抛光液中的pH引起。覆盖晶片上的材料层较好的是:钨、铜、铝、一种电介质材料或上述材料的组合。
本发明的另一个实施例是对半导体基片上的材料层进行化学机械抛光的抛光方法。所述方法包括下述步骤:
将一含有过氧化物的物质和一稳定剂与一种抛光液混合,形成一种抛光液混合物;
将所述抛光液混合物储存一个期间;使用所述抛光液混合物和一台化学机械抛光装置,对半导体基片上的材料层进行平面加工;
所述稳定剂可以包括选自下述的化合物:焦磷酸钠的十水合物,焦磷酸,多磷酸,多膦酸,乙二胺四乙酸,焦磷酸盐,多磷酸盐,多膦酸盐,乙二胺四乙酸盐,8-羟基喹啉以及由上述化合物组成的任一种混合物。较好的是,所述稳定剂还可使用焦磷酸钠的十水合物。
图1所示为过氧化氢随时间的分解情况图。其中,过氧化氢作为氧化剂与W2000抛光液混合。
图2所示为混合有稳定剂的W2000抛光液中的过氧化氢随时间的分解情况图。所述稳定剂为本发明上述实施例中所用之一种。
图3所示为混合有本发明的另一实施例中的稳定剂的W2000抛光液中的过氧化氢浓度说明图。
图4所示为混合有本发明的一优选实施例中的稳定剂的W2000抛光液中的过氧化氢浓度说明图。
图5所示为混合有本发明的另一优选实施例中的稳定剂的W2000抛光液中的过氧化氢浓度说明图。
以下,参照一个使用过氧化氢的钨CMP方法详细说明本发明。本发明可以被用于任一个其中使用含有过氧化物抛光液的CMP方法。例如,除了钨之外,可以利用于去除其它的导体材料。事实上,所须去除的材料可以是一种电介质材料,而不是导体材料。另外,可以使用任何一种稳定剂,只要所述稳定剂具有下述特性即可:
(1)所述稳定剂具有在一水性或有机介质中与过渡金属(这些金属包括,但并不限于,如Fe、Cu、Co、Mn、Ni及Cr的元素)的结合性能;
(2)所述稳定剂基本上不含有过渡金属杂质;
(3)所述稳定剂可溶解于含有过氧化物的抛光液混合物中;
(4)所述稳定剂并不影响在以CMP方法作抛光处理时的材料层的抛光速率;
(5)所述稳定剂部分显著改变用于CMP抛光液中的磨料粒度。
这些稳定剂的举例包括:焦磷酸,多磷酸,多膦酸,乙二胺四乙酸(EDTA),上述酸的盐,上述酸及上述酸盐的混合物及羟基喹啉。进一步,所述抛光液中还可以含有过渡金属杂质。
下述图表说明了由Cabot Corporation(称为“W2000”)开发、用于抛光含钨材料层得的抛光液中的过氧化氢浓度随时间的变化。参见图1,曲线102表示用在W2000抛光液中未经稳定的过氧化氢浓度变化。如图1所示,过氧化氢在加入于W2000抛光液中9日之后,其浓度约为起始混合时的60%。
图2及图3显示:例如,EDTA、EDTA的盐,膦酸及羟基喹啉等的各种螯合剂,并不是一定能提供所需的过氧化氢稳定性。事实上,各种所试验的螯合剂加快了过氧化氢的分解。然而,这些螯合剂的一种或二种以上(单独使用,或相互结合使用或与另一种其它的化学品结合使用)可能提供适当的稳定性,其条件是:其使用量不同,经过提纯,以除去如过渡金属等的任何杂质,用于另一种抛光液,或者与另一种化学品物质(这些化学品本身可能是或不是稳定剂)结合使用。一个本领域的普通技术人员根据本发明说明书的教导,将能够实现这些条件,而无须进行过多的试验工作。
图4表明本发明的一个优选实施例的稳定过程(表示为曲线402)。其中,过氧化氢的起始浓度较好的是基于过氧化氢和W2000抛光液总重量的2%。在这个实施例中,稳定剂的使用量较好的是:对每2000g抛光液混合物加入约2g的焦磷酸钠,根据所使用的特定的钨CMP方法中的力学特征,过氧化氢的下限浓度约为1.5%。焦磷酸钠的使用量可以不同,以提供更好的对过氧化氢的稳定性。如果使用了不同的抛光液,则适宜的稳定剂使用量会不同,甚至需用不同的稳定剂。
图5说明本发明的其它优选实施例稳定剂的几种不同的用量。其中,过氧化氢的起始浓度较好的是基于过氧化氢和W2000抛光液总重量的约4%。在这个实施例中,稳定剂的用量较好的是:对每1000g抛光液混合物用约0.25g~3g,更好的是用约0.25g~1g,特别好的是用约0.5g的范围。由于所使用的特定钨的CMP方法中的力学特性,过氧化氢的下限浓度约为3.8%。焦磷酸钠的使用量可以不同,以提供更好的稳定性。如果使用了不同的抛光液,则适宜的稳定剂用量会不同,甚至需用不同的稳定剂。
尽管,在此对本发明的一些具体实施例作了说明,但它们并不是对本发明范围的限制。对那些本领域的技术人员来说,显而易见的是,参照本发明说明书所揭示的方法,可以得到其它实施例。本发明的范围仅限于权利要求书所所要求的范围。
Claims (12)
1.一种电气器件的制造方法,所述电气器件具有一覆盖在半导体基片上的结构,所述基片使用化学机械平面加工方法进行平面加工,其特征在于,所述方法包括下述步骤:
提供一半导体晶片;
在半导体晶片上形成一材料层,所述材料层材料选自钨、铜、铝、电介质材料及这些材料的任一种组合;
将所述晶片置于一抛光垫上,使用抛光液对其材料层进行抛光,所用抛光液含有过氧化物和过渡金属;
使用选自焦磷酸、焦磷酸盐及上述化合物的任一混合物的稳定剂,对所述抛光液进行稳定化,所述稳定剂阻止过氧化物在含有上述过渡金属的抛光液中的分解。
2.如权利要求1所述的电气器件的制造方法,其特征在于,所述稳定剂包括选自多磷酸、多膦酸、乙二胺四乙酸、多磷酸盐、多膦酸盐、乙二胺四乙酸盐及上述化合物的任一混合物。
3.如权利要求1所述的电气器件的制造方法,其特征在于,所述稳定剂包括8-羟基喹啉。
4.如权利要求1所述的电气器件的制造方法,其特征在于,所述焦磷酸盐为焦磷酸钠的十水合物。
5.如权利要求1所述的电气器件的制造方法,其特征在于,所述抛光液中过氧化物的分解是由所述抛光液中的pH引起的。
6.如权利要求1所述的电气器件的制造方法,其特征在于,所述稳定剂以对所述抛光液总量1000克使用0.25-1克。
7.一种电气器件的制造方法,所述电气器件具有一覆盖在半导体基片上的结构,所述基片使用化学机械平面加工方法进行平面加工,其特征在于,所述方法包括下述步骤:
提供一半导体晶片;
在所述半导体晶片上形成一材料层,所述材料层材料选自钨、铜、铝、电介质材料及这些材料的任一种组合;
将所述晶片置于一抛光垫上,使用抛光液对其材料层进行抛光,所用抛光液含有过氧化物和过渡金属;
使用包括焦磷酸钠的十水合物的稳定剂对所述抛光液进行稳定化,所述稳定剂可阻止过氧化物在含有上述过渡金属的抛光液中的分解。
8.一种电气器件的制造方法,所述电气器件具有一覆盖在半导体基片上的结构,所述基片使用化学机械平面加工方法进行平面加工,其特征在于,所述方法包括下述步骤:
提供一半导体晶片;
在所述半导体晶片上形成一材料层,所述材料层材料选自钨、铜、铝、电介质材料及这些材料的任一种组合;
将所述晶片置于一抛光垫上,使用抛光液对其材料层进行抛光,所用抛光液含有过氧化物和过渡金属;
使用焦磷酸钠的十水合物和选自焦磷酸、多磷酸、多膦酸、乙二胺四乙酸、多磷酸盐、多膦酸盐、乙二胺四乙酸盐、上述化合物的任一混合物及其他的焦磷酸盐的稳定剂,对抛光液进行稳定化;所述稳定剂可阻止过氧化物在含有上述过渡金属的抛光液中的分解。
9.一种对半导体基片上的材料层进行化学机械抛光的抛光方法,其特征在于,所述方法包括下述步骤:
将所述含有过氧化物的物质和稳定剂与抛光液混合,形成一含有过渡金属的抛光液混合物;
储存所述抛光液混合物一定期间;
使用所述抛光液混合物和化学机械抛光装置对置于所述半导体基片上的材料层进行抛光,所述材料层材料选自钨、铜、铝、电介质材料及这些材料的任一种组合;
所述稳定剂可阻止含有过氧化物的物质在上述含有过渡金属的抛光液中的分解,所述稳定剂选自焦磷酸、焦磷酸盐及其任何混合物。
10.如权利要求9所述的电气器件的制造方法,其特征在于,所述焦磷酸盐为焦磷酸钠的十水合物。
11.一种对半导体基片上的材料层进行化学机械抛光的抛光方法,其特征在于,所述方法包括下述步骤:
将所述含有过氧化物的物质和稳定剂与抛光液混合,形成一含有过渡金属的抛光液混合物;
储存所述抛光液混合物一定期间;
使用所述抛光液混合物和化学机械抛光装置对置于所述半导体基片上的材料层进行抛光,所述材料层材料选自钨、铜、铝、电介质材料及这些材料的任一种组合;
所述稳定剂可阻止含有过氧化物的物质在上述含有过渡金属的抛光液中的分解,所述稳定剂包括焦磷酸钠的十水合物。
12.如权利要求9所述的电气器件的制造方法,其特征在于,所述稳定剂以对所述抛光液总量1000克使用0.25-1克。
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US6448182B1 (en) | 2002-09-10 |
US6530967B1 (en) | 2003-03-11 |
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KR20000035614A (ko) | 2000-06-26 |
TW593644B (en) | 2004-06-21 |
WO2000032713A1 (en) | 2000-06-08 |
CN1255521A (zh) | 2000-06-07 |
ATE484561T1 (de) | 2010-10-15 |
KR100626768B1 (ko) | 2006-09-25 |
AU2032200A (en) | 2000-06-19 |
SG73683A1 (en) | 2000-06-20 |
JP2000164541A (ja) | 2000-06-16 |
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