CN1221810A - 清洗衬底的方法和清洗液 - Google Patents

清洗衬底的方法和清洗液 Download PDF

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CN1221810A
CN1221810A CN98125072A CN98125072A CN1221810A CN 1221810 A CN1221810 A CN 1221810A CN 98125072 A CN98125072 A CN 98125072A CN 98125072 A CN98125072 A CN 98125072A CN 1221810 A CN1221810 A CN 1221810A
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和气智子
青木秀充
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Abstract

对其上形成有构图的金属层的衬底进行清洗的方法,包括使用具有螯合作用的清洗液从衬底上除去金属杂质的步骤。清洗液为包括具有螯合作用的羧酸的水溶液。水溶液含有水溶性羧酸、铵基羧酸和具有氨基的羧酸中的一个。水溶性羧酸为乙酸、蚁酸、柠檬酸和乙二酸中的一个。构图的金属层由过渡金属和过滤金属的化合物中的一个与Si(硅)、N(氮)和O(氧)中的一个制成。

Description

清洗衬底的方法和清洗液
本发明一般涉及构图的金属层于其上的衬底的清洗方法,特别涉及除去粘附到衬底的金属杂质的清洗方法和清洗液,通过精细和高密度构图金属层已形成在衬底上。
近些年来,随着器件变得越来越密集,对具有薄膜多层结构的衬底,例如用于电子器件的半导体衬底、液晶衬底、印制衬底,和具有磁性材料的衬底进行多层膜的精细处理。
特别是,半导体器件变得高度密集,它的栅电极制作的很精细。因此,低阻硅化物材料(WSix,TiSix)或如钨(W)等的金属材料或具有TiN、WN夹在W或WSix膜或TiSix膜之间的多层结构用做栅电极材料。
图1示出了薄膜晶体管的示意性结构。栅氧化膜(SiO2)2形成在Si(硅)衬底1上,金属膜淀积在栅氧化膜2上。通过干腐蚀精细地构图金属膜形成栅电极3。此后,源区4和漏区5通过离子注入形成在衬底1内。
在这些步骤中,如Fe、Al等的金属杂质由干腐蚀装置和离子注入机产生,并粘附到栅氧化膜2的表面。栅氧化膜2上的金属杂质6在随后的热处理步骤中通过栅氧化膜2扩散到Si衬底1内。这使得漏电流容易在栅电极3下的沟道区域内产生,或减少了源区和漏区之间最大允许电压,导致器件可靠性下降。
因此,有必要在干腐蚀栅氧化膜2上的金属膜后和离子注入之后,从栅氧化膜2的表面除去金属杂质6,进行使用酸性清洗液的清洗处理,以便从栅氧化膜2的表面上除去这些步骤期间产生的金属杂质6。
通常,在使用Si衬底的半导体工艺中,SPM(硫酸与过氧化氢混合溶液)或HPM(盐酸、过氧化氢与去离子水混合溶液)主要用做除去金属杂质的清洗液。
液晶和印制衬底很少用酸性溶液清洗,可以用如IPA(异丙醇)等的有机溶液清洗。
然而,除去金属杂质使用的常规酸性清洗液(SPM,HPM)存在可能会腐蚀构成栅电极3的材料的问题。
特别是,用做低阻栅使用的金属布线材料中的TiN和W容易被这些酸性溶液腐蚀,所以不能使用它们进行清洁处理。
如图2A所示,例如,栅电极3为由多层膜组成的DRAM栅电极,其中多晶硅层7形成在栅氧化膜2上,硅化物(TiSix)层8和氮化膜(TiN)9随后淀积在多晶硅层7上。如果使用清洗液SPM或HPM除去干腐蚀或离子注入之后产生的金属杂质,那么氮化膜(TiN)8的侧壁被腐蚀,如图2B所示,所以不能保持多层结构,并且栅电极和布线可能会除去。
此外,当能有效地除去金属的DHF(氟酸与水系统与去离子水混合溶液)用做清洁溶液时,硅化物层(TiSix)9被大量地腐蚀,也栅氧化膜(SiO2)2也被腐蚀,所以也不能使用DHF。
如上所述,随着半导体器件的集成度的提高,栅电极的宽度也制作得很精细,所以由常规酸性清洗液处理而被腐蚀的材料量不能忽略,因此需要能够除去金属杂质同时不会腐蚀低阻金属材料的清洗液。
鉴于这些情况完成本发明,本发明的目的是提供一种在清洗衬底的处理中,从衬底的表面除去金属杂质同时不腐蚀形成其上的任何构图的金属材料的清洗方法,以及在该方法中使用的清洗液。
根据本发明,用与如铁(Fe)、铝(Al)等的金属具有螯合作用水溶液作为除去金属杂质的清洗液。具体地,具有整合作用的羧酸可以用做清洗液。即,清洗液可以包括含下面一种水溶性羧酸的水溶液组成:例如醋酸、蚁酸、柠檬酸、草酸、羧酸铵和具有氨基的羧酸。将螯合剂添加到具有螯合作用的羧酸中,以增强与金属的螯合。
根据本发明的清洗方法包括用清洗液从具有构图金属层的衬底表面除去金属杂质的步骤。
构成构图金属层的材料是Ti(钛)、W(钨)、Co(钴)、Ni(镍)或Ta(钽)、或这些过渡金属中的每一个与Si(硅)、N(氮)或O(氧)构成的化合物,由此可以可靠地除去金属杂质并且不会腐蚀构图的金属层。
例如,在栅氧化膜形成在半导体衬底上然后栅电极形成其上的情况中,羧酸和氨基添加到清洗液中形成与如Fe、Al等的金属螯合的螯合物,由此可以除去粘附到栅氧化膜的金属杂质。
在这种情况中的金属杂质经常以金属氧化物或金属原子的形式被化学地或物理地吸收到氧化膜表面。根据本发明,吸收的金属杂质可以容易地通过螯合作用被捕获并除去。
另一方面,栅电极的金属材料金属形成牢固的金属间键合,所以通过清洗液的螯合作用断裂并除去这种键合的可能性没有或很小。因此,即使根据本发明的清洁溶液用于清洗处理,也很难腐蚀部分栅电极。
图1为示出薄膜场效应晶体管的一个例子;
图2A为用常规清洗液进行清洗处理之前具有多层栅电极形成在栅氧化膜上的薄膜场效应晶体管的另一个例子;
图2B为用常规清洗液进行清洗处理之后图2A的薄膜场效应晶体管;
图3为示出使用SPM、HPM和根据本发明实施例的清洗液的各例中TiN膜的腐蚀速率图形;
图4为示出根据本发明实施例的清洗液、SPM和HPM除去Fe杂质效果的对比图形;
图5A为用根据本发明实施例的清洗液进行清洗处理之前具有多层栅电极形成在栅氧化膜上的薄膜场效应晶体管的一个例子;
图5B为根据实施例用清洗液进行清洗处理之后图5A的薄膜场效应晶体管。
下文介绍使用根据本发明清洗液的一个例子和使用清洗液的清洗方法。
本发明人发现添加螯合剂的乙二酸(1%)的水溶液(下面用1%乙二酸的水溶液表示)适于从衬底表面除去金属杂质并且不腐蚀形成在衬底上的金属层。
具体地,将下面螯合剂中的一个添加到1%乙二酸浓度的水溶液中:如乙二胺四乙酸(EDTA)和反式-1,2环己二胺四乙酸(CyDTA)等的氨基多羧酸;如1,2-乙二胺四(亚甲基膦酸)(EDTPO)、1,2-乙二胺二(亚甲基膦酸)(EDDPO)、次氮基三(亚甲基膦酸)(NTPO)和1-羟基亚乙基-1,1’-二膦酸(HEDPO)等的膦酸;如三膦酸和六甲基膦酸等的稠膦酸;如1,2-乙二胺和三乙醇胺等的胺;如卤化物离子(F-、Cl-、Br-、I-)、氰化物离子、硫氰酸离子、硫代硫酸盐离子和铵离子等的无机离子的化合物;以及它们的铵盐。但优选使用EDTA、CyDTA、EDTPO、EDDPO、NTPO和HEDPO。
仅使用具有螯合作用的羧酸例如乙二酸制成清洗液。在该实施例中,要增强螯合作用,选自以上螯合剂的一个螯合剂添加到乙二酸溶液(1%)中。更具体地说,EDTA被用作螯合剂,将30ppm的EDTA添加到乙二酸溶液(1%)中以形成清洗液(1%乙二酸水溶液)。
如图3所示,分别测量该清洗液(1%的乙二酸水溶液)和常规清洗液SPM和HPM对TiN膜的腐蚀速率,结果显示在图3中。TiN膜用做DRAM的多层栅中的子层。
从图3可以看出,常规使用的清洗液SPM和HPM对TiN膜显示出高达6nm/min以上的极高腐蚀速率,分别由参考数字301和302表示。
另一方面,用螯合剂添加到乙二酸水溶液(1%)的本发明清洗液显示出0.1nm/min以下的腐蚀速率,由参考数字303表示,因此很难发生腐蚀。
然后,检查该清洗液(1%的乙二酸水溶液)和常规使用的清洗液SPM和HPM清除Fe杂质的效果。
如图4所示,用每种清洗液对粘附有金属杂质(Fe杂质)的Si衬底(硅晶片)进行清洁处理,清洁处理之后测量表面上的Fe浓度。结果显示在图4中。
参考图4,清洗处理之前Fe浓度约5×1012个原子/cm2,由标号401表示。用螯合剂添加到乙二酸水溶液(1%)的清洗液清洗之后5×1012个原子/cm2的初始Fe浓度可以减少到1010个原子/cm2以下,由标号402表示。用常规清洗液SPM和HPM清洗处理可以得到类似的效果,分别用标号403和404表示。
通过图3和4显示的测量结果可以看出通过用螯合剂添加到乙二酸水溶液(1%)的清洗液进行清洗处理可以除去表面上残留的金属杂质(Fe杂质),并且不腐蚀TiN膜。
现在介绍用螯合剂添加到乙二酸水溶液(1%),即1%的乙二酸水溶液的清洗液清洗半导体衬底的方法。
参考图5A,硅衬底1上淀积5nm厚的栅氧化膜2,然后在其上形成栅电极3或构图的金属层。具体地,以下面的顺序在栅氧化膜2上依次形成100nm厚的poly-Si膜(多晶硅膜)7、10nm厚的TiN(氮化钛)膜8、和200nm的TiSix膜9。此后,通过干腐蚀构图这些层形成多层的栅电极3。
如前所述,由于多层膜的干腐蚀,Fe杂质留在栅氧化膜2的表面上。
干腐蚀后要从栅氧化膜2上除去金属杂质,使用清洗液(1%的乙二酸水溶液)进行5分钟的清洗处理。由于TiN膜8的侧面腐蚀量可以控制到0.5nm以下,所以与处理之前相比,清洗处理之后很难改变栅电极3的截面形状,如图5B所示。
相反,如果使用常规的清洗液(HPM)进行5分钟的清洗处理,那么TiN膜8的腐蚀速率特别快,所以在TiN膜8的侧面发生30nm的侧蚀,如图2B所示,不能保持栅电极3的多层结构。因此,存在可能除去TiSi膜(硅化物材料)9的情况。
对于清洗处理的结果,干腐蚀之后留在栅氧化膜2表面上的Fe杂质可以从3×1011原子/cm2的级别减小到1×1010原子/cm2以下的级别,该级别等同于用常规溶液进行清洗处理得到的结果。
根据以上介绍的实施例,用清洗液(1%的乙二酸水溶液)清洗其上形成有栅电极3的半导体衬底,由此抑制了栅电极材料的腐蚀。因此,栅电极3的形状由此得到保持,同时除去了金属杂质并且没有降低器件的可靠性。
此外,可以从半导体衬底(硅晶片)的整个表面上除去金属杂质,所以在制备半导体器件的随后的工艺中,抑制了交叉污染,高可靠性器件的制造是进行的。
虽然在以上介绍的例子中使用乙二酸的水溶液作为清洗液,但也可以是如乙酸、蚁酸、柠檬酸等的水溶性羧酸。此外,可以使用含这些羧酸和具有氨基的羧酸中一个的铵盐。
虽然作为要清洗的栅电极的一个例子介绍了具有多层结构(这里为TiSix/TiN)的栅电极3,暴露在衬底上的金属不限于电极或布线的特定部分。根据本发明的清洗处理也对已形成构图的金属层于其上的衬底有效。
用做金属层的金属类型可以是过渡金属,例如Ti(钛)、W(钨)、Co(钴)、Ni(镍)或Ta(钽)、或这些过渡金属的每个与Si(硅)、N(氮)或O(氧)构成的化合物。此外,也可以是TiSix、TiN、TiOx、WNx、WOx、CoSix、CoNx、NiSix、NiNx、NiOx、TaSix、TaNx、或TaOx。以上介绍的任意金属或化合物都可以用做构成栅电极3的材料,以便粘附到衬底的金属杂质可靠地除去,同时在本发明的清洗处理中不腐蚀栅电极。
因此,通过从栅氧化膜上除去金属杂质,对晶体管的开关特性有负面影响的栅电极的腐蚀不会发生,也可以防止在晶体管的结产生漏电流。
根据本发明,用含有水溶性羧酸、铵基羧酸和具有氨基的羧酸中的一个的水溶液对衬底进行清洗处理,可以除去衬底上残留的金属杂质,同时不腐蚀形成在衬底上的金属层。

Claims (20)

1.一种清洗其上形成有构图金属层的衬底的方法,特征在于包含使用具有螯合作用的清洗液从衬底上除去金属杂质的步骤。
2.根据权利要求1的方法,其中清洗液为包括具有螯合作用的羧酸的水溶液。
3.根据权利要求2的方法,其中水溶液还包括螯合剂。
4.根据权利要求2或3的方法,其中水溶液含有水溶性羧酸、羧酸铵和具有氨基的羧酸之一。
5.根据权利要求4的方法,其中水溶性羧酸为乙酸、甲酸、柠檬酸和乙二酸之一。
6.根据权利要求1-3任一权利要求的方法,其中构图的金属层由过渡金属和过渡金属与Si(硅)、N(氮)和O(氧)之一形成的化合物之一制备。
7.根据权利要求6的方法,其中过渡金属选自Ti(钛)、W(钨)、Co(钴)、Ni(镍)和Ta(钽)。
8.根据权利要求1-3任一权利要求的方法,其中构图的金属层具有包括多层金属子层的多层结构。
9.根据权利要求1-3任一权利要求的方法,其中每个金属子层由过渡金属和过渡金属与Si(硅)、N(氮)和O(氧)之一形成的化合物之一制备。
10.根据权利要求9的方法,其中过渡金属选自Ti(钛)、W(钨)、Co(钴)、Ni(镍)和Ta(钽)之一。
11.根据权利要求1-3任一权利要求的方法,其中在衬底上构图金属层形成构图的金属层的干腐蚀步骤之后进行除去金属杂质的步骤。
12.根据权利要求1-3任一权利要求的方法,其中在离子注入步骤之后进行除去金属杂质的步骤。
13.一种清洗其上形成有构图金属层的衬底的清洗液,特征在于包括具有螯合作用的水溶液。
14.根据权利要求13的清洗液,其中清洗液为包括具有螯合作用的羧酸的水溶液。
15.根据权利要求14的清洗液,其中水溶液还包括螯合剂。
16.根据权利要求14或15的清洗液,其中水溶液含有水溶性羧酸,羧酸铵和具有氨基的羧酸之一。
17.根据权利要求16的方法,其中水溶性羧酸为乙酸、甲酸、柠檬酸和乙二酸之一。
18.根据权利要求13-15的任何一个权利要求的清洗液,其中构图的金属层由过渡金属和过渡金属与Si(硅)、N(氮)和O(氧)之一形成的化合物之一制备。
19.根据权利要求13-15的任何一个权利要求的清洗液,其中构图的金属层具有包括多层金属子层的多层结构。
20.根据权利要求19的清洗液,其中每个金属子层由过渡金属和过渡金属与Si(硅)、N(氮)和O(氧)之一形成的化合物之一制备。
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