CN101097862A - 形成电容器电介质的方法以及使用该电容器电介质制造电容器的方法 - Google Patents

形成电容器电介质的方法以及使用该电容器电介质制造电容器的方法 Download PDF

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CN101097862A
CN101097862A CNA2006101564350A CN200610156435A CN101097862A CN 101097862 A CN101097862 A CN 101097862A CN A2006101564350 A CNA2006101564350 A CN A2006101564350A CN 200610156435 A CN200610156435 A CN 200610156435A CN 101097862 A CN101097862 A CN 101097862A
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deposition
oxide layers
tantalum oxide
zirconia layer
purge gas
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CN100550317C (zh
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朴钟范
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SK Hynix Inc
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Abstract

一种形成电容器电介质的方法，包括沉积氧化锆层、在氧化锆层上实施后处理使得氧化锆层具有四方相和在氧化锆层上沉积氧化钽层使得氧化钽层具有四方相。

Description

形成电容器电介质的方法以及使用该电容器电介质制造电容器的方法
交叉引用的相关申请
本发明要求享有在2006年6月29日提交的韩国专利申请No.10-2006-005998的优先权，通过引用将其全部内容并入本文。
技术领域
本发明涉及制造半导体器件的方法，更具体涉及形成具有氧化锆层和氧化钽层的电容器电介质的方法以及使用该电容器电介质制造电容器的方法。
背景技术
氧化铪(HfO2)/氧化铝(Al2O3)/氧化铪的层叠结构通常被用作金属-绝缘体-金属(MIM)电容器中的电容器电介质，用来提高电容量并使漏电流最小化。氧化铪是具有结晶相的高介电常数的材料，氧化铝是具有无定形相的低介电常数的材料。
图1是传统电容器结构的截面图。传统电容器包括下电极11、布置在下电极11上的具有HfO2/Al2O3/HfO2层叠结构的电容器电介质12和布置在电容器电介质12上的上电极13。
氧化铪增加电容器电介质12中的介电常数。但是，当氧化铪结晶时，漏电流性能特征劣化。因此，在传统的电容器结构中应该小心地使氧化铪结晶，以实现有利的漏电流性能特征。
此外，当使用氧化铪作为电容器电介质时，通过氧化铪可增加的电容量可受到限制。因此，当电容器的设计尺寸(design rule)减少时，难以将氧化铪应用于电容器电介质。
发明内容
本发明的具体实施方案提供一种用于形成具有氧化锆层和氧化钽层的电容器电介质的方法。氧化锆层和氧化钽层均具有四方相。所得电容器电介质具有有利的漏电流性能特征以及高介电常数。还提供一种使用所披露的电容器电介质来制造电容器的方法。
根据本发明的一方面，形成电容器电介质的方法包括沉积氧化锆层。在氧化锆层上实施后处理，使得氧化锆层具有四方相。在氧化锆层上方沉积具有四方相的氧化钽层。
根据本发明的另一方面，形成电容器电介质的方法包括沉积氧化钽层。在氧化钽层上实施后处理，使得氧化钽层具有四方相。在氧化钽层上方沉积具有四方相的氧化锆层。
根据本发明的又一方面，制造电容器的方法包括形成下电极。在下电极上方形成电容器电介质。电容器电介质包括具有四方相的氧化锆层和具有四方相的氧化钽层。在电容器电介质上方形成上电极。
根据本发明的又一方面，一种电容器包含下电极。在下电极上方形成电容器电介质，其中电容器电介质包括具有四方相的氧化锆层和具有四方相的氧化钽层。在电容器电介质上方形成上电极。
附图说明
图1是传统电容器结构的截面图。
图2是根据本发明第一实施方案的电容器结构的截面图。
图3是根据本发明第二实施方案的电容器结构的截面图。
图4A～4C图示说明制造根据本发明第一实施方案的电容器的方法。
图5A～5C图示说明制造根据本发明第二实施方案的电容器的方法。
具体实施方式
图2图示说明根据本发明第一实施方案的电容器的截面图。根据第一实施方案的电容器包括下电极21、布置在下电极21上的电容器电介质100和布置在电容器电介质100上的上电极24。电容器电介质100包括氧化锆层(ZrO2)22A和氧化钽层(Ta2O5)23。氧化锆层22A和氧化钽层23顺序堆叠在下电极21上。
图3是根据本发明第二实施方案的电容器结构的截面图。根据本发明第二实施方案的电容器包括下电极31，沉积在下电极31上的电容器电介质200和沉积在电容器电介质200上的上电极34。电容器电介质200由氧化钽层32A和氧化锆层33构成。氧化钽层32A和氧化锆层33顺序堆叠在下电极31上。
在图2和3中，用于各电容器电介质100和200的氧化锆层22A和33以及氧化钽层23和32A均具有四方相。因此，氧化锆层22A和33以及氧化钽层23和32A分别以附图标记T-ZrO2和T-Ta2O5来表示。
实施原子层沉积过程以获得四方相。四方相可以在氧化锆和氧化钽层的两个沉积过程之间利用臭氧(O3)处理来获得。下面详细说明形成电容器电介质的方法。
下电极21和31以及上电极24和34各自包括金属电极。每一个电极均由选自下列材料中的一种制成：氮化钽(TiN)、钌(Ru)、铂(Pt)、铱(Ir)和氮化铪(HfN)。
图4A～4C图示说明制造根据本发明第一实施方案的电容器的方法。参考图4A，形成下电极21。下电极21包括金属电极。具体地，下电极由选自下列材料中的一种制成：TiN、Ru、Pt、Ir和HfN。利用氢氟酸或缓冲氧化物蚀刻剂来清洗下电极21的表面。
将形成有下电极21的晶片载入将实施原子层沉积过程的室中。在约0.1托～约10托的室压力和约250℃～约350℃的过程温度下实施氧化锆层22的沉积。
重复实施原子层沉积过程直到氧化锆层22具有所需的预定厚度。具体地，通过重复单元沉积循环来实施原子层沉积过程。单元沉积循环包括：将具有下电极21的衬底载入沉积室中；引入锆源；引入清洗气体；引入反应物以及再次引入清洗气体。
在将衬底载入沉积室中后，将锆源引入室中，使其吸附在下电极21上。锆源使用选自下列物质的前体：Zr[NC2H5CH3]4、Zr[OC(CH3)2CH2OCH3]4、Zr[OC(CH3)3]4、ZrCl4和ZrI4。锆源流动约0.1～10秒。
将清洗气体引入沉积室中以从沉积室中去除没有吸附在下电极表面上的所有未反应的锆源。惰性气体(例如Ar、He、N2气体等及其组合)被用作清洗气体。清洗气体流动约0.1～10秒。
将反应物引入沉积室中。反应物包括O3或O2等离子体。反应物流动约0.1～10秒。
再次将清洗气体引入沉积室中，以去除所有未反应的反应物以及所有副产物。惰性气体被用作清洗气体，清洗气体流动约0.1～10秒。
通过重复上述单元沉积循环，氧化锆层在下电极21上沉积到所需厚度。在一个实施方案中，所需厚度为约40～约100。参考图4B，在沉积氧化锆层22之后，在氧化锆层22上实施臭氧处理，使得氧化锆层22具有四方相。臭氧处理在约300℃～约500℃的过程温度下实施。另外，臭氧浓度为约180g/m3～约300g/m3。下文中，具有四方相的氧化锆层22被称为T-氧化锆层(T-ZrO2)22A。
参考图4C，在T-氧化锆层22A上沉积氧化钽层23。利用上述原子层沉积过程来沉积厚度约20～约100的氧化钽层23。原子层沉积过程在约0.1托～约10托的室压力以及约250℃～约350℃的过程温度下实施。下面详细说明氧化钽层23的沉积方法。
重复实施原子层沉积过程直到氧化钽层23具有所需的预定厚度。具体地，通过在沉积室中重复单元沉积循环来实施原子层沉积过程。单元沉积循环包括：将钽源引入到其上形成有T-氧化锆层22A的衬底上；引入清洗气体；引入反应物以及再次引入清洗气体。
钽源被引入到沉积室中，吸附在T-氧化锆层22A上。钽源使用氯化钽(TaCl5)前体。钽源流动约0.1～10秒。
清洗气体被引入沉积室中以去除没有吸附在T-氧化锆层22A表面上的所有未反应的钽源。惰性气体(例如Ar、He、N2气等及其组合)被用作清洗气体。清洗气体流动约0.1～10秒。
将反应物引入沉积室中。反应物包括O3或O2等离子体。反应物流动约0.1～10秒。
再次将清洗气体引入沉积室中，以去除所有未反应的反应物和副产物。惰性气体被用作清洗气体，清洗气体流动约0.1～10秒。
通过重复上述单元沉积循环，氧化钽层23在T-氧化锆层22A上沉积到所需厚度。在一个实施方案中，所需厚度为约20～约100。
当如上所述沉积氧化钽层23时，氧化钽层23具有四方相。换言之，当在具有四方相的T-氧化锆层22A上沉积氧化钽层23时，氧化钽层23也具有四方相。下文中，具有四方相的氧化钽层被称为T-氧化钽层(T-Ta2O5)。
图5A～5C图示说明用于制造根据本发明第二实施方案的电容器的方法。参考图5A，形成下电极31。在一个实施方案中，下电极31包括金属。具体地，下电极31由选自下列材料中的一种制成：TiN、Ru、Pt、Ir和HfN。利用氢氟酸或缓冲氧化物蚀刻剂来清洗下电极31的表面。
将形成有下电极31的晶片载入将实施原子层沉积过程的室中。在约0.1托～约10托的室压力和约250℃～约350℃的过程温度下实施氧化钽层32的沉积。
利用原子层沉积过程在下电极31上沉积厚度约20～约100的氧化钽层32。原子层沉积过程在约0.1托～约10托的室压力和约250℃～约350℃的过程温度下实施。下面详细说明氧化钽层32的沉积方法。
重复实施原子层沉积过程直到氧化钽层32具有所需的预定厚度。具体地，通过重复单元沉积循环来实施原子层沉积过程。单元沉积循环包括：将钽源引入到沉积室中；引入清洗气体；引入反应物以及再次引入清洗气体。
钽源被引入到沉积室中，使其吸附在下电极31上。在一个实施方案中，钽源使用氯化钽(TaCl5)前体。钽源流动约0.1～10秒。
清洗气体被引入沉积室中以去除所有未反应的残留钽源。未反应的钽源可包括没有吸附在下电极31的表面上的钽源。惰性气体(例如Ar、He、N2气等及其组合)被用作清洗气体。清洗气体流动约0.1～10秒。
将反应物引入沉积室中。反应物包括O3或O2等离子体。反应物流动约0.1～10秒。
再次将清洗气体引入沉积室中，以去除所有未反应的反应物和副产物。惰性气体被用作清洗气体，清洗气体流动约0.1～10秒。
通过重复单元沉积循环，氧化钽层32在下电极31上沉积到所需厚度。在一个实施方案中，氧化钽层32的所需厚度为约20～约100。
在沉积氧化钽层32之后，实施臭氧处理，以提供具有四方相的氧化钽层32，如图5B中所示。在一个实施方案中，臭氧处理在约300℃～约500℃的过程温度和约180g/m3～约300g/m3的臭氧浓度下实施。臭氧处理之后，氧化钽层32被转化为具有四方相的氧化钽(T-Ta2O5)。
接着，参考图5C，在T-氧化钽层32A上沉积氧化锆层33。
下面将说明利用原子层沉积过程的氧化锆层的沉积方法。重复实施原子层沉积过程直到氧化锆层22具有所需的预定厚度。具体地，通过重复单元沉积循环来实施原子层沉积过程。单元沉积循环包括：将形成有T-氧化钽层32A的衬底载入沉积室中；引入锆源；引入清洗气体；引入反应物以及再次引入清洗气体。
在将衬底载入沉积室中后，将锆源引入室中，使其吸附在T-氧化钽层32A上。在一个实施方案中，锆源使用选自下列物质的前体：Zr[NC2H5CH3]4、Zr[OC(CH3)2CH2OCH3]4、Zr[OC(CH3)3]4、ZrCl4和ZrI4。锆源流动约0.1～10秒
将清洗气体引入沉积室中以从沉积室中去除所有未反应的锆源。未反应的锆源可包括没有吸附在T-氧化钽层32A表面上的所有锆源。惰性气体(例如Ar、He、N2气体等及其组合)被用作清洗气体。清洗气体流动约0.1～10秒。
将反应物引入沉积室中。反应物可包括O3或O2等离于体。反应物流动约0.1～10秒。
再次将清洗气体引入沉积室中，以去除所有未反应的反应物和副产物。惰性气体被用作清洗气体，清洗气体流动约0.1～10秒。
通过重复上述单元沉积循环，氧化锆层33在T-氧化钽层32A上沉积到所需厚度。在一个实施方案中，所需厚度为约40～约100。
当如上所述沉积氧化锆层33时，氧化锆层33具有四方相。换言之，当在具有四方相的T-氧化钽层32A上沉积氧化锆层33时，氧化锆层33也具有四方相。
在所述实施方案中，原位实施氧化锆层的沉积、臭氧处理和氧化钽层的沉积。
根据上述实施方案，电容器电介质构成具有Ta2O5/ZrO2或ZrO2/Ta2O5的双层，而不是多层堆叠的层例如传统的具有HfO2/Al2O3/HfO2的三层。在本发明实施方案中，沉积具有预定厚度的第一介电层即氧化锆层(或氧化钽层)。实施臭氧处理以提供具有四方相的第一介电层。随后，在经臭氧处理的第一介电层上沉积第二介电层即氧化钽层(或氧化锆层)，使得第二介电层也具有四方相。换言之，通过在预定温度下在经臭氧处理的具有四方相的第一介电层上沉积第二介电层，在第一介电层上沉积具有四方相的第二介电层。例如，如果在T-氧化锆层上沉积氧化钽层，则在T-氧化锆层上形成的氧化钽层也具有四方相。
当氧化锆层和氧化钽层均具有四方相时，它们提供了比其它相的氧化锆层和氧化钽层更好的漏电流性能特征。
四方相的氧化锆层的介电常数几乎是立方相的两倍。具体地，立方相的氧化锆层的介电常数为约23。但是四方相的则具有约40的介电常数。因此，提高了漏电流性能特征。
此外，可获得比传统电容器电介质更高的电容量。同样，无定形相的氧化钽层具有约20的介电常数，而其结晶时则具有约25～约50的介电常数。因此，提高了氧化钽层的电容量。
当通过依次实施第一介电层的沉积、臭氧处理和第二介电层的沉积来形成电容器电介质时，可以通过控制过程温度和每一个介电层的厚度来形成具有四方相的电容器电介质。因此，可形成能够提供高电容量以及优异的漏电流性能特征的电容器电介质。
如上所述，根据本发明，氧化锆层和氧化钽层的层叠结构被用作电容器电介质。在两个沉积过程之间实施臭氧处理，使得氧化锆层和氧化钽层均具有四方相。四方相提高了漏电流性能特征并增加了电容量。
在一个实施方案中，由于高的介电常数，氧化锆层和氧化钽层的层叠结构具有约9或更小的有效氧化物厚度。因此，即使设计尺寸减小，也可保证足够的电容量。
虽然已经关于具体实施方案说明了本发明，但显而易见的是，对本领域技术人员而言，可以在不偏离如所附权利要求所限定的本发明精神和范围的情况下做出各种变化和修改。

Claims (44)

1.一种形成电容器电介质的方法，所述方法包括：
在衬底上沉积氧化锆层；
在氧化锆层上实施后处理，使得氧化锆层具有四方相；和
在氧化锆层上沉积氧化钽层，使得氧化钽层具有四方相。
2.权利要求1的方法，其中后处理包括臭氧处理。
3.权利要求1的方法，其中后处理包括在约300℃～约500℃的温度下利用约180g/m3～约300g/m3的氧浓度来实施的氧处理，所述氧处理包括臭氧的使用。
4.权利要求1的方法，其中利用原子层沉积过程来实施氧化锆层的沉积和氧化钽层的沉积。
5.权利要求4的方法，其中通过重复单元沉积循环来实施氧化锆层的原子层沉积过程，直到氧化锆层具有约40～约100的厚度，所述单元沉积循环包括引入锆源、引入第一清洗气体、引入反应物以及引入第二清洗气体。
6.权利要求5的方法，其中锆源使用选自以下物质的前体：Zr[NC2H5CH3]4、Zr[OC(CH3)2CH2OCH3]4、Zr[OC(CH3)3]4、ZrCl4和ZrI4，而且其中锆源流动约0.1～10秒，其中第一清洗气体和第二清洗气体是相同类型的。
7.权利要求4的方法，其中通过重复单元沉积循环来实施氧化钽层的原子层沉积过程，直到氧化钽层具有约20～约100的厚度，所述单元沉积循环包括引入钽源、引入第一清洗气体、引入反应物和引入第二清洗气体，其中第一清洗气体和第二清洗气体是相同类型的。
8.权利要求7的方法，其中钽源使用氯化钽前体，而且其中钽源流动约0.1～10秒。
9.权利要求5的方法，其中反应物包括O3和O2等离子体中的一种。
10.权利要求5的方法，其中第一清洗气体和第二清洗气体各自包括惰性气体。
11.权利要求1的方法，其中在约250℃～约350℃的温度下和在约0.1托～约10托的压力下实施氧化锆层的沉积和氧化钽层的沉积。
12.权利要求1的方法，其中原位实施氧化锆层的沉积、后处理和氧化钽层的沉积。
13.一种形成电容器电介质的方法，所述方法包括：
在衬底上沉积氧化钽层；
在氧化钽层上实施后处理，以提供具有四方相的氧化钽层；和
在氧化钽层上沉积氧化锆层，使得氧化锆层具有四方相。
14.权利要求13的方法，其中后处理包括使用臭氧。
15.权利要求14的方法，其中后处理在约300℃～约500℃的温度下、在约180g/m3～约300g/m3的氧浓度的环境中实施。
16.权利要求13的方法，其中利用原子层沉积过程来实施氧化钽层的沉积和氧化锆层的沉积。
17.权利要求16的方法，其中通过重复单元沉积循环来实施氧化锆层的原子层沉积过程，直到氧化锆层具有约40～约100的厚度，所述单元沉积循环包括引入锆源、引入第一清洗气体、引入反应物和引入第二清洗气体。
18.权利要求17的方法，其中锆源使用选自以下物质的前体：Zr[NC2H5CH3]4、Zr[OC(CH3)2CH2OCH3]4、Zr[OC(CH3)3]4、ZrCl4和ZrI4，而且其中锆源流动约0.1～10秒。
19.权利要求16的方法，其中通过重复单元沉积循环来实施氧化钽层的原子层沉积过程，直到氧化钽层具有约20～约100的厚度，所述单元沉积循环包括引入钽源、引入第一清洗气体、引入反应物和引入第二清洗气体。
20.权利要求19的方法，其中钽源使用氯化钽前体，而且其中钽源流动约0.1～10秒。
21.权利要求19的方法，其中反应物包括O3和O2等离子体中的一种。
22.权利要求19的方法，其中第一清洗气体和第二清洗气体各自包括惰性气体。
23.权利要求19的方法，其中在约250℃～约350℃的温度下和在约0.1托～约10托的压力下实施氧化钽层的沉积和氧化锆层的沉积。
24.权利要求13的方法，其中原位实施沉积氧化钽层的步骤、后处理步骤和沉积氧化锆层的步骤。
25.一种制造电容器的方法，所述方法包括：
在衬底上形成下电极；
在下电极上形成电容器电介质，其中电容器电介质包括具有四方相的氧化锆层和具有四方相的氧化钽层；和
在电容器电介质上形成上电极。
26.权利要求25的方法，其中形成电容器电介质包括：
沉积氧化锆层；
在氧化锆层上实施后处理，使得氧化锆层具有四方相；和
在氧化锆层上沉积氧化钽层，使得氧化钽层具有四方相。
27.权利要求25的方法，其中形成电容器电介质包括：
沉积氧化钽层；
在氧化钽层上实施后处理，使得氧化钽层具有四方相；和
在氧化钽层上沉积氧化锆层，使得氧化锆层具有四方相。
28.权利要求26的方法，其中后处理包括使用臭氧。
29.权利要求26的方法，其中后处理包括使用氧，其中在约300℃～约500℃的温度下、在约180g/m3～约300g/m3的氧浓度环境中实施处理。
30.权利要求26的方法，其中利用原子层沉积过程来实施氧化锆层的沉积和氧化钽层的沉积。
31.权利要求30的方法，其中通过重复单元沉积循环来实施氧化锆层的原子层沉积过程，直到氧化锆层具有约40～约100的厚度，所述单元沉积循环包括引入锆源、引入第一清洗气体、引入反应物和引入第二清洗气体。
32.权利要求31的方法，其中锆源使用选自以下物质的前体：Zr[NC2H5CH3]4、Zr[OC(CH3)2CH2OCH3]4、Zr[OC(CH3)3]4、ZrCl4和ZrI4，而且其中锆源流动约0.1～10秒。
33.权利要求30的方法，其中通过重复单元沉积循环来实施氧化钽层的原子层沉积过程，直到氧化钽层具有约20～约100的厚度，所述单元沉积循环包括引入钽源、引入第一清洗气体、引入反应物和引入第二清洗气体。
34.权利要求33的方法，其中钽源使用氯化钽前体，而且其中钽源流动约0.1～10秒。
35.权利要求30的方法，其中在约250℃～约350℃的温度下和在约0.1托～约10托的压力下实施氧化锆层的沉积和氧化钽层的沉积。
36.权利要求26的方法，其中原位实施沉积氧化钽层的步骤、后处理步骤和沉积氧化锆层的步骤。
37.权利要求27的方法，其中利用原子层沉积过程来实施氧化锆层的沉积和氧化钽层的沉积。
38.权利要求37的方法，其中通过重复单元沉积循环来实施氧化锆层的原子层沉积过程，直到氧化锆层具有约40～约100的厚度，所述单元沉积循环包括引入锆源、引入第一清洗气体、引入反应物和引入第二清洗气体。
39.权利要求38的方法，其中锆源使用选自以下物质的前体：Zr[NC2H5CH3]4、Zr[OC(CH3)2CH2OCH3]4、Zr[OC(CH3)3]4、ZrCl4和ZrI4，而且其中锆源流动约0.1～10秒。
40.权利要求37的方法，其中通过重复单元沉积循环来实施氧化钽层的原子层沉积过程，直到氧化钽层具有约20～约100的厚度，所述单元沉积循环包括引入钽源、引入第一清洗气体、引入反应物和引入第二清洗气体。
41.权利要求40的方法，其中钽源使用氯化钽前体，而且其中钽源流动约0.1～10秒。
42.权利要求37的方法，其中在约250℃～约350℃的温度下和在约0.1托～约10托的压力下实施氧化锆层的沉积和氧化钽层的沉积。
43.权利要求37的方法，其中原位实施沉积氧化钽层的步骤、后处理步骤和沉积氧化锆层的步骤。
44.一种电容器，包含：
下电极：
形成在下电极上的电容器电介质，其中所述电容器电介质包括具有四方相的氧化锆层和具有四方相的氧化钽层；和
形成在电容器电介质上的上电极。
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