CN1708364A - 采用超临界二氧化碳/化学制剂去除图案化硅/二氧化硅上的粒子污染物 - Google Patents
采用超临界二氧化碳/化学制剂去除图案化硅/二氧化硅上的粒子污染物 Download PDFInfo
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Abstract
一种用于从半导体基片上的微小区域去除微粒污染物的清洗组合物。该组合物含有超临界二氧化碳(SCCO2)、醇、氟源和任选的羟基添加剂。此种清洗组合物克服了SCCO2作为清洗剂的固有缺陷,即SCCO2的非极性特性及与其相关的不能溶解诸如无机盐和极性有机化合物类型的物质,所述类型的物质以微粒污染物形式存在于晶片基片上并且为了有效清洗必须从半导体基片上除去。该清洗组合物能实现Si/SiO2基片上带有微粒污染物的基片的无损伤、无残留物清洗。
Description
发明领域
本发明涉及基于超临界二氧化碳的组合物,在半导体制造中用于从其上具有粒子污染物的图案化硅/二氧化硅基片上去除粒子污染物,并涉及采用此类组合物从半导体基片上去除粒子污染物的方法。
相关技术描述
在半导体制造领域,采用了各种晶片清洁方法用以去除粒子污染物。举几个例子,这些方法包括超声、高压喷射洗涤、受激准分子激光烧蚀以及二氧化碳雪喷(snow-jet)技术。
近来对采用空气从半导体基片吹走粒子,以及清洗时的流体喷射动力学作了广泛研究。
迄今所有开发的方法均具有相关联的缺陷。
更普遍地,伴随从半导体基片去除污染物粒子而存在的问题包括:表面污染物特性上可能是有机和/或无机的,因而从选择相容性清洁试剂的观点来看,清洁过程变得复杂化。另外,并非所有的表面都是光滑的,由于之前的蚀刻和/或沉积过程而可能带有不同程度的粗糙度,从而使清洁过程复杂化。另外,存在着一些影响污染物粒子去除的粘附力,例如范德华吸引力、静电相互作用、重力和化学相互作用。因此,流动特性、化学和物理状况均有所涉及,使微粒污染物的去除复杂化。
由于从晶片表面去除粒子污染物对于确保作为半导体制造工艺最终产品的微电子设备的准确操作,以及避免制造工艺中涉及随后处理步骤的干扰或缺陷极为重要,因而对于清洁技术的改进领域存在着持续的需求。
发明概述
本发明涉及基于超临界二氧化碳的组合物,在半导体制造中用于从其上具有粒子污染物的图案化硅/二氧化硅基片上去除粒子污染物,并涉及采用此类组合物从半导体基片上去除粒子污染物的方法。
本发明的一方面涉及粒子污染物清洗组合物,含有SCCO2,醇,氟源以及任选地羟基添加剂。
本发明的另一方面涉及粒子污染物清洗组合物,含有SCCO2,甲醇,氟化铵,氟化的表面活性剂以及硼酸,其中基于清洗组合物的总重,甲醇的浓度为约5-约20重量%,氟化物的浓度为约0.01-约2.0重量%,硼酸的浓度为约0.01-约2.0重量%。
本发明的另一方面涉及从其上带有粒子污染物的基片上去除粒子污染物的方法,所述方法包含在充分接触条件下,将粒子污染物与清洗组合物接触充分时间,使粒子污染物从基片上除去,所述清洗组合物含有SCCO2,醇,氟源以及任选地羟基添加剂。
本发明的其他方面,特征和实施方案将从后续公开内容和所附权利要求而更清晰了解。
附图简述
图1是含有图案化的二氧化硅层和硅层的晶片的光学显微镜照片,显示了以SCCO2/甲醇溶液清洗后晶片上的SiN污染物粒子。
图2是图1中所示类型的晶片以含有SCCO2,甲醇和氟化铵和硼酸的清洗组合物清洗后的光学显微镜照片。
图3是图1中所示类型的晶片以含有SCCO2,甲醇和氟化的表面活性剂的清洗组合物清洗后的光学显微镜照片。
图4是图1中所示类型的晶片以含有SCCO2,甲醇,氟化铵,硼酸和氟化的表面活性剂的清洗组合物清洗后的光学显微镜照片。
发明详述和优选实施方案
本发明基于的发现是基于超临界二氧化碳的清洗组合物,所述清洗组合物对于从其上存在有污染物粒子的半导体基片去除污染物粒子极有效力。本发明的组合物和方法有效用于从空白和图案化晶片的硅和二氧化硅区域去除表面粒子,所述表面粒子包括有机和/或无机组成的粒子。
超临界二氧化碳(SCCO2)由于同时具有液体和气体的特性,因而乍一看可能就被当作用于去除微粒污染物的理想试剂。与气体类似,它能快速扩散,具有低粘度,接近于零的表面张力,以及容易地穿透入沟槽和通孔。而与液体类似,其作为“洗涤”介质又具有整体流动能力。
尽管具有这些表面上的优点,然而超临界CO2是非极性的。因此,它不能溶解许多种类的物质,包括许多以污染物粒子存在并且为了有效清洗必须从半导体基片除去的无机盐和极性有机化合物。因此,SCCO2的非极性特性对其用于晶片表面污染物粒子的清洗形成了阻碍。
在本发明提供的基于SCCO2的组合物中,超临界CO2的这一缺陷已被本发明所克服,所述基于SCCO2的组合物对于从空白和图案化晶片的硅和二氧化硅区域清洗粒子极有效,并可实现其上带有此类污染物粒子的基片的无损伤、无残留物清洗。
更特别地,本发明构思出一种粒子污染物清洗组合物,包括SCCO2,醇,氟源,以及任选地羟基添加剂。
本发明的组合物对于从半导体基片上的微小区域上清洗粒子污染物具有效用,而不会另外侵蚀Si/SiO2晶片的含Si区域。
在清洗组合物中,氟源辅助去除存在于Si/SiO2表面上的硅杂质。氟源可以是任意的合适类型,例如含氟化合物或其他氟种类。示例性的氟源组分包括氟化氢(HF),三氢氟化三乙胺或通式为NR3(HF)3的其他三氢氟化胺化合物其中R各自独立地选自氢和低级烷基(C1-C8烷基),氟化氢-吡啶(pyr-HF),以及通式为R4NF的氟化铵其中R各自独立地选自氢和低级烷基(C1-C8烷基),等等。在本发明组合物中,氟化铵(NH4F)是目前优选的氟源,但采用任意其他合适的氟源组分可达到同等的成效。
本组合物还可包括在该组合物中提供额外的氟和氟化物的氟化的表面活性剂。
任选的羟基添加剂用于保护晶片免受另外的氧化作用。尽管为此目的可方便地采用诸如3-羟基-2-萘甲酸的其他羟基试剂,但目前优选的羟基添加剂是硼酸。另外,羟基添加剂也可以是氟源,例如2-氟苯酚等。
作为清洗组合物的溶剂相,用于形成SCCO2/醇溶液的醇可以是任意的合适类型。在本发明一个实施方案中,此类醇包含C1-C4醇(即甲醇、乙醇、丙醇或丁醇),或两种或多种此类醇的混合物。
在优选实施方案中,该醇是甲醇。所存在的醇类助溶剂与SCCO2一道用于增加组合物对以微粒污染物形式存在的无机盐和极性有机化合物的溶解性。通常,SCCO2和醇类彼此相关的特定比例和用量可适当地改变,以提供SCCO2/醇溶液对微粒污染物的理想溶解(溶剂化)作用,这在本领域技能内无需过多努力即可容易地确定。基于组合物总重,醇的浓度范围可以为约5-约20重量%。
在一个实施方案中,本发明的清洗组合物包括SCCO2,醇,氟化铵,氟化的表面活性剂以及硼酸。
在此种特性的优选组合物中,作为特别适合于Si/SiO2晶片表面清洗的组合物,基于清洗组合物的总重,氟化铵的存在浓度为约0.01-约1.0重量%,硼酸的存在浓度为约0.01-约1.0重量%。
可在约1000-约7500psi的压力范围下,采用本清洗组合物与其上带有微粒污染物的基片接触足够的时间,以实现微粒污染物从基片的理想去除,例如持续约5-约30分钟的接触时间范围,且温度范围为约35-约100℃,尽管在有充分理由的情况下,在本发明广泛实践中可有利地采用更高或更低的接触持续时间和温度。
在一个实施方案中,在分别为55℃和4000psi的温度和压力下,采用30分钟的处理时间(10分钟动态流动,10分钟静态浸泡,10分钟动态流动,然后是三个体积的SCCO2/甲醇(20重量%)冲洗和三个体积的纯SCCO2冲洗),通过SCCO2/醇(15重量%)/氟化物(0.55重量%)溶液实现了SiN粒子从Si/SiO2基片的尤其高度的去除。
特别优选实施方案中的清洗过程包括顺序处理步骤,包含:清洗组合物动态流过其上带有微粒污染物的基片,然后基片静态浸泡于清洗组合物中,在此交替步骤的循环中,分别交替和重复地实施动态流动和静态浸泡步骤。
例如,在前述30分钟接触时间的示例实施方案中,可对动态流动/静态浸泡步骤实施三个连续循环,依次包括10分钟的动态流动,10分钟的静态浸泡和10分钟的动态流动。
将清洗组合物与具有微粒污染物的基片接触之后,此后在第一洗涤步骤中优选地以大量SCCO2/醇溶液(不含任何其他组分)例如20%甲醇溶液洗涤基片,用以从已实现了微粒污染物去除的基片区域去除任何残留的沉淀化学添加剂,最后在第二洗涤步骤中以大量的纯SCCO2洗涤基片,用以从基片区域去除任何残留的醇类助溶剂和/或沉淀的化学添加剂。
通过如下讨论的经验性成就和结果可更完全地展示本发明的特征和优点。
在此研究中检测的样品晶片包括存在于图案化的二氧化硅层和硅层上的氮化硅粒子。首先在50℃和4400psi条件下采用纯SCCO2对样品进行处理,并且虽然流量(10mL/min)的速度除去了一些粒子,但并不能有效地完全除去所有污染粒子。
图1是含有图案化的二氧化硅层和硅层的该晶片的光学显微镜照片,显示了以SCCO2/甲醇溶液清洗之后晶片上的SiN污染物粒子。
然后将各种化学添加剂/表面活性剂添加入SCCO2/甲醇溶液中,并检测其去除粒子的效力。
图2所示为50℃下以SCCO2/甲醇/硼酸/NH4F溶液清洗的晶片的光学图象,清晰示出SiN粒子已被从SiO2表面除去,然而,该清洗溶液不能将粒子从硅区域有效除去。所使用的硼酸用来保护SiO2表面免受氟离子的侵蚀,同时与二氧化硅表面形成氢键,以辅助最可能由范德华力保持的粒子的脱离。氟源用来通过与SiN粒子的化学反应而辅助粒子的去除,由此辅助粒子从晶片表面的去除。暴露于湿气下不产生HF的共价氟源通常对于从硅表面去除粒子是理想的。
图3是图1中所示类型的晶片以含有SCCO2,甲醇和氟化的表面活性剂的清洗组合物清洗后的光学显微镜照片。从图3可看出,SCCO2/甲醇/氟化的表面活性剂溶液并没有从SiO2表面除去粒子。
图4是图1中所示类型的晶片以含有SCCO2,甲醇,氟化铵,硼酸和氟化的表面活性剂的清洗组合物清洗后的光学显微镜照片,图中表明此种组合物成功地将表面粒子从整个图案化的晶片上除去。
因此,上述照片证明了根据本发明的清洗组合物对于去除晶片基片上的微粒污染物的效力。
本发明的清洗组合物可通过各成分的简易混合而容易制得,例如在轻微搅拌下在混合容器中混合。
一旦制剂化,即将此类清洗组合物施用至基片,用于例如在以合适的体积流率和量供给有清洗组合物的加压接触腔内,在合适的高压下与基片上面的残留物接触,以实现所需的接触操作,用于蚀刻后残留物的去除。
可以理解,基于此处的公开内容,本发明清洗组合物用的特定接触条件可在本技术的技能之内容易地确定,本发明清洗组合物中各成分的特定比例及各成分浓度可作广泛改变而仍可达到蚀刻后残留物从基片的所需去除。
因此,尽管此处已描述了本发明的特定方面、特征和示例性实施方案,但应理解本发明的应用并不受限于此,而应拓展至并包含诸多其他方面、特征和实施方案。因此,后述的权利要求则应相应广泛地解释为包括本发明主旨和范围内的所有此类方面、特征和实施方案。
Claims (24)
1.蚀刻后残留物清洗组合物,含有SCCO2、醇、氟源以及任选的羟基添加剂。
2.权利要求1的组合物,其中醇含有至少一种C1-C4醇。
3.权利要求1的组合物,其中醇含有甲醇。
4.权利要求1的组合物,其中氟源含有选自如下的含氟化合物:氟化氢(HF);通式为NR3(HF)3的三氢氟化胺化合物,其中R各自独立地选自氢和低级烷基;氟化氢-吡啶(pyr-HF);以及通式为R4NF的氟化铵,其中R各自独立地选自氢和低级烷基。
5.权利要求1的组合物,其中氟源含有氟化铵(NH4F)。
6.权利要求1的组合物,其中羟基添加剂含有硼酸。
7.权利要求1的组合物,其中羟基添加剂羟基添加剂也是所述氟源的至少一部分。
8.权利要求1的组合物,其中羟基添加剂羟基添加剂和氟源含有2-氟苯酚。
9.权利要求1的组合物,其中基于组合物总重,所述醇具有的浓度范围为约5-约20重量%。
10.权利要求1的组合物,其中基于清洗组合物总重,氟源具有的浓度为约0.01-约2.0重量%
11.权利要求1的组合物,含有氟化铵、氟化的表面活性剂及硼酸。
12.权利要求11的组合物,其中基于清洗组合物的总重,氟化铵具有的浓度为约0.1-约2.0重量%。
13.粒子污染物的清洗组合物,含有SCCO2、甲醇、氟化铵、氟化的表面活性剂和硼酸,其中基于清洗组合物的总重,甲醇浓度为约5-约20重量%,氟化物浓度为约0.01-约2.0重量%,硼酸浓度为约0.01-约2.0重量%。
14.从其上具有粒子污染物的基片去除粒子污染物的方法,所述方法包含在充分接触条件下,将含有SCCO2、醇、氟源及任选的羟基添加剂的清洗组合物与粒子污染物接触充分时间,将粒子污染物从基片除去。
15.权利要求14的方法,其中所述接触条件包含高压。
16.权利要求15的方法,其中所述高压包含约1000-约7500psi的压力范围。
17.权利要求14的方法,其中所述接触时间为约5-约30分钟的时间范围。
18.权利要求14的方法,其中的氟源含有选自如下的含氟化合物:氟化氢(HF);通式为NR3(HF)3的三氢氟化胺化合物,其中R各自独立地选自氢和低级烷基;氟化氢-吡啶(pyr-HF);以及通式为R4NF的氟化铵,其中R各自独立地选自氢和低级烷基。
19.权利要求14的方法,其中氟源含有氟化铵(NH4F)。
20.权利要求14的方法,其中所述组合物含有SCCO2、甲醇、氟化铵、氟化的表面活性剂和硼酸,其中基于清洗组合物的总重,甲醇浓度为约5-约20重量%,氟化物浓度为约0.01-约2.0重量%,硼酸浓度为约0.01-约2.0重量%。
21.权利要求14的方法,其中所述接触步骤含有清洗循环,包括:(i)清洗组合物与蚀刻后残留物的动态流动接触,以及(ii)清洗组合物与蚀刻后残留物的静态浸泡接触。
22.权利要求21的方法,其中所述清洗循环含有交替和重复实施的蚀刻后残留物的动态流动接触(i)与静态浸泡接触(ii)。
23.权利要求22的方法,其中所述清洗循环包含按顺序实施(i)动态流动接触和(ii)静态浸泡接触,并对所述顺序重复三次。
24.权利要求14的方法,进一步包含在第一洗涤步骤中以SCCO2/醇洗涤溶液、在第二洗涤步骤中以SCCO2对微粒污染物已被去除的基片区域进行洗涤的步骤,用以在所述第一洗涤步骤中除去残留的沉淀的化学添加剂,并在所述第二洗涤步骤中除去残留的沉淀的化学添加剂和/或残留的醇。
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AU2003288966A8 (en) | 2004-06-07 |
WO2004042794B1 (en) | 2004-09-23 |
EP1559132A2 (en) | 2005-08-03 |
KR20050075758A (ko) | 2005-07-21 |
EP1559132A4 (en) | 2007-04-11 |
TW200408699A (en) | 2004-06-01 |
WO2004042794A2 (en) | 2004-05-21 |
JP2006505139A (ja) | 2006-02-09 |
CN100346887C (zh) | 2007-11-07 |
US20040087456A1 (en) | 2004-05-06 |
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