CN101098954A - 不含氟化物的离子注入光致抗蚀剂去除用超临界流体组合物 - Google Patents
不含氟化物的离子注入光致抗蚀剂去除用超临界流体组合物 Download PDFInfo
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Abstract
本发明所述为从具有离子注入光致抗蚀剂的半导体基片去除此类光致抗蚀剂的方法和组合物。该去除组合物含有供去除离子注入光致抗蚀剂所用的超临界CO2(SCCO2)、共溶剂和还原剂。此类去除组合物克服了SCCO2作为去除试剂的固有缺陷,即SCCO2的非极性特性和与之相关的对存在于光致抗蚀剂中的、为有效清洗必须从半导体基片除去的物质不具有溶解能力,所述物质例如无机盐和极性有机化合物。
Description
发明领域
本发明涉及不含氟化物的超临界流体(SCF)基组合物,其在半导体制造中用于从具有光致抗蚀剂的基片去除此类光致抗蚀剂,包括离子注入光致抗蚀剂,并涉及采用该组合物从半导体基片去除离子注入光致抗蚀剂的方法。
相关技术描述
随着半导体器件越来越集成化和小型化,离子注入已被更加广泛地采用,用来精确控制半导体基片中的杂质分布。在该处理过程中,通常将图案化的光致抗蚀剂用于离子的选择性注入。
光致抗蚀剂层包括聚合材料或树脂和作为光敏化合物的敏化剂。采用掩膜将光致抗蚀剂层部分暴露于紫外(UV)光,然后使光致抗蚀剂层显影,得到图案化的抗蚀剂层。使用该图案化的抗蚀剂层,从而在离子注入过程中下面的基片仅选定部分被注入离子。在半导体器件的制造中重要的一点是,离子注入之后、下一步骤开始之前必须将抗蚀剂层除去。
但是,当将光致抗蚀剂置于高剂量的离子注入处理,如>1×1015原子/cm2,则会使光致抗蚀剂表面的氢耗尽,从而使光致抗蚀剂转变成坚硬、碳化、高度交联的外壳。去除硬化的光致抗蚀剂的常规方法包括氧等离子灰化法,其通常与卤素气体结合,从而穿透外壳并除去光致抗蚀剂。通常,等离子灰化处理要求以湿化学物和/或稀酸进行后续的清洗,用以除去残存的残留物和/或非挥发性污染物,从而确保微电子器件的准确操作,以及避免制造工艺中与后续处理步骤相关的干扰或缺陷。
上述灰化和湿清洗操作在其应用过程中遭遇一系列的问题和缺陷,包括:
(1)在硬化的外壳下面,本体光致抗蚀剂中受热的残留溶剂蒸发,从而导致光致抗蚀剂从基片表面爆裂(导致半导体基片的相关污染);
(2)由于存在注入光致抗蚀剂中的、经等离子灰化处理未完全除去的非挥发性金属化合物,从而导致残留金属污染的发生;
(3)尽管使用了等离子灰化和湿化学处理,但仍产生残存于半导体基片上的(聚合外壳或高交联聚合物的)硬质残留物;
(4)需要重复的清洗步骤,其增加了光致抗蚀剂剥离的循环次数和在产品(work-in-process)步骤;和
(5)须处置相当量的湿化学物和/或稀酸。
为开发从半导体基片去除离子注入硬化光致抗蚀剂和其残留物的改进配方,人们在半导体制造工业中进行了相当大的和持续的努力。但临界尺寸持续和快速的减少使这一努力屡受挫折。随着临界尺寸(CD)宽度减至100nm以下,包含水基组合物的常规湿化学法因清洗溶液中所用液体的高表面张力特性而受到相当的限制。另外,水性清洗溶液可强烈影响多孔低k介电材料的重要材料性能,包括机械强度、水分摄取、热膨胀系数和对不同基片的附着性。
超临界流体(SCF)提供了从半导体表面去除光致抗蚀剂的替换性方法。SCFs扩散快,粘度低,表面张力近于零,并能容易地透入深的沟槽和通孔。另外,SCFs因其低粘度而可快速传送溶解的物质。但SCFs是高度非极性的,因此许多物质在SCFs中溶解均不充分。
因此若能提供从半导体基片去除离子注入光致抗蚀剂的有效SCF基组合物,该SCF基组合物克服了常规去除组合物和方法的上述缺陷,则将是本领域内的一个显著进步。
发明简述
本发明涉及不含氟化物的SCF基组合物,其用于从具有光致抗蚀剂的基片去除此类光致抗蚀剂,包括离子注入光致抗蚀剂。本发明还涉及采用该SCF基组合物从半导体基片去除离子注入光致抗蚀剂的方法。
一方面,本发明涉及离子注入光致抗蚀剂去除组合物,其包括至少一种SCF、至少一种共溶剂和至少一种还原剂。
另一方面,本发明涉及从具有离子注入光致抗蚀剂的基片去除此类光致抗蚀剂的方法,所述方法包括使具有离子注入光致抗蚀剂的基片与SCF基组合物在充分接触条件下接触充分长时间,从而从基片去除离子注入光致抗蚀剂,所述SCF基组合物包括至少一种SCF、至少一种共溶剂和至少一种还原剂。
从下文内容和所附权利要求会更清楚全面地了解本发明的其他方面、特征和实施方式。
附图简述
图1是控制晶片的光学图像,所述控制晶片含有高剂量离子注入光致抗蚀剂。
图2是图1晶片在70℃、3000psi用超临界二氧化碳(SCCO2)/异丙醇(IPA)/甲酸溶液进行清洗之后的光学图像,其显示光致抗蚀剂完全被除去,周围的SiO2层仅有轻微蚀刻。
发明详述及优选实施方式
本发明是基于如下发现:不含氟化物的超临界流体(SCF)基组合物可用于从具有光致抗蚀剂的基片去除此类光致抗蚀剂,包括离子注入光致抗蚀剂。具体而言,本发明涉及采用本文所述SCF基组合物从图案化的半导体晶片去除离子注入光致抗蚀剂。
超临界二氧化碳(SCCO2)因易于制造,没有毒性,对环境影响轻微,因而在本发明的广泛实施中是优选的SCF,尽管本发明可以用任何合适的SCF类物质来实施,具体SCF的选择取决于所涉及的特定应用。其他优选的可用于本发明实施的SCF类物质包括氧、氩、氪、氙和氨。本发明后文的一般性描述中具体提及SCCO2时,是为了提供本发明的说明性实例,而不意味着对本发明作任何方式的限制。
SCCO2作为用于从半导体晶片表面去除多余物质和/或层的试剂是具有吸引力的,因为SCCO2兼具液体和气体的特性。象气体一样,它扩散快,粘度低,表面张力接近于零,而且容易透入深的沟槽和通孔。象液体一样,它作为“洗涤”介质具有总体流动能力。
尽管超临界CO2具有这些表面上的优点,但它是非极性的。因而它不能溶解许多为充分清洗必须从半导体基片除去的离子性或极性物质,包括无机盐和极性光致抗蚀剂材料。因而在半导体器件的制造中,SCCO2非极性的特性阻碍了其在进一步处理步骤之后于去除光致抗蚀剂中的应用。
然而本发明基于的发现是,通过使不含氟化物的SCCO2基去除组合物合适地配制有下文充分描述的添加剂,可克服与SCCO2和其他SCFs的非极性相关的缺点,与之伴随的发现是,以SCCO2基去除介质从基片去除光致抗蚀剂和离子注入光致抗蚀剂具有高度有效性,且实现了从其上具有光致抗蚀剂的基片如离子注入的图案化半导体晶片无损害、无残留物地去除所述光致抗蚀剂。
一方面,本发明涉及不含氟化物的SCCO2基组合物,其用于从半导体基片去除离子注入光致抗蚀剂。本发明的配方包括SCCO2、至少一种共溶剂和至少一种还原剂,所述组分基于组合物总重按如下含量范围存在:
组分 | 重量% |
SCCO2 | 约60.0%-约90.0% |
共溶剂 | 约10.0%-约30.0% |
还原剂 | 约0.01%-约5.0% |
在本发明广泛实践中,SCCO2基组合物包括如下,或由如下组成,或基本由如下组成: SCCO2、至少一种共溶剂和至少一种还原剂。
SCCO2中加入共溶剂起到增加组合物对光致抗蚀剂和离子注入光致抗蚀剂类物质的溶解性的作用,其增溶方式是相比于单独的SCCO2,该组合物对光致抗蚀剂的去除能力具有显著的改进。SCCO2基去除组合物中所用的共溶剂优选为醇。在本发明的一个实施方式中,此类醇包括直链或支链C1-C6醇(即甲醇、乙醇、异丙醇等),或者两种或多种上述醇的混合物。在本发明另一实施方案中,所述共溶剂是胺,包括单乙醇胺和三乙醇胺。在优选实施方案中,所述醇是异丙醇(IPA)。
采用本文所述的SCF基组合物时,加入还原剂改进了对离子注入光致抗蚀剂的去除效果。SCF基组合物中所用的还原剂包括甲酸、氢气、甲醛、福尔马林、硼烷、乙硼烷、胺稳定化的硼烷(R3N·BH4)(其中R是直链或支链C1-C4烷基)、胺稳定化的铝烷(R3N·AlH3)(其中R是直链或支链C1-C4烷基)、BH4和AlH4的四烷基胺(其中烷基是直链或支链C1-C4基)和其他产氢化合物。
一般而言,SCCO2、共溶剂和还原剂彼此之间的特定比例和用量可适当地改变,从而提供SCCO2/共溶剂/还原剂组合物对将要从基片清洗去的光致抗蚀剂和离子注入光致抗蚀剂的期望溶解(溶剂化)作用。对上述特定比例和用量,本领域技术人员无需过多努力通过简易实验即可容易确定。
在待除去的光致抗蚀剂与SCCO2基组合物接触时,使用升高的温度条件可增强SCCO2/共溶剂/还原剂组合物的去除效果。
任选地可将本发明的SCCO2基去除组合物配制有其他组分,从而进一步增加组合物的去除能力,或改进组合物的特性。因此,该组合物可配制有稳定剂、螯合剂、氧化抑制剂、络合剂等等。
在一个实施方式中,本发明的SCF基组合物包括SCCO2、IPA和甲酸。
在另一方面,本发明涉及采用本文描述的SCCO2基组合物从半导体晶片表面去除光致抗蚀剂的方法,所述光致抗蚀剂包括离子注入光致抗蚀剂。
本发明的SCCO2基组合物通过(i)最大程度地减少所需化学试剂的用量,从而减少废物的量,和(ii)最大程度地减少残留物爆裂和污染的形成,同时提供了具有可循环成分如SCFs的组合物和方法,从而克服了现有技术中离子注入光致抗蚀剂去除方法的不足之处。
可在约1500psi-约4500psi的压力范围下,将合适的SCCO2基组合物与具有离子注入光致抗蚀剂的晶片表面接触充分时间,从而实现对光致抗蚀剂的期望去除,例如接触时间范围为约1分钟至约20分钟,温度为约30℃至约100℃,尽管在本发明的广泛实践中,在允许的情况下,可有利地使用更长/高或更短/低的接触持续时间和温度。在优选的实施方式中,接触温度范围为约50℃-约90℃,优选约70℃。
在本发明实践中,通过将温度改变至特定值、并在该温度测定由SCCO2基组合物从基片去除的光致抗蚀剂材料量,可容易地经验确定特定的升温和温度范围对去除光致抗蚀剂的性质和程度的效果。以此方式,对本发明特定SCCO2基组合物而言,可确定其对特定的待去除光致抗蚀剂材料的最优温度水平。
以类似方式,可选择除温度外的工艺条件,本领域内确定的最优或有利条件包括超临界流体组合物与待从基片去除的离子注入光致抗蚀剂接触时的表压、SCCO2基组合物接触的流动和/或静态特性,以及接触的持续时间。
可使SCCO2基组合物在含离子注入光致抗蚀剂的晶片表面动态流动或静态浸泡,从而对含光致抗蚀剂的晶片表面进行处理。
“动态”接触方式包括所述组合物在晶片表面上连续地流动,从而使传质梯度最大化并实现光致抗蚀剂从该表面的完全去除。“静态浸泡”接触方式包括使晶片表面与静态体积的所述组合物接触,并保持与之接触一个连续的(浸泡)时间段。
在特别优选的实施方式中,去除过程包括顺序的处理步骤,包括:SCCO2基组合物在含离子注入光致抗蚀剂的晶片表面上动态流动,接着是该晶片静态地浸泡在该SCCO2基组合物中,在此交替步骤的循环中,各动态流动步骤和静态浸泡步骤交替、重复地进行。
例如,所述动态流动/静态浸泡步骤在上述说明性的实施方式中可以被连续地执行4个循环,包括如下顺序:2.5min-10min的动态流动,2.5min-5min的高压静态浸泡,例如约3000psi-约4500psi,2.5min-10min的动态流动,和2.5min-10min的低压静态浸泡,例如约1500psi-约2900psi。在优选的实施方式中,所述顺序由5min的动态流动和3000-4500psi下5min的静态浸泡组成。
在SCCO2基组合物和晶片表面接触之后,晶片优选地在第一洗涤步骤中用大量的SCF/醇溶液洗涤,从而从已经去除了粒子的晶片表面区域除去任何沉淀的残留化学添加剂,并最后在第二洗涤步骤中用大量的纯SCF洗涤以去除晶片表面任何残留的甲醇和/或沉淀的化学添加剂。优选地,用于洗涤的SCF是SCCO2。
本发明SCCO2基组合物的共溶剂/还原剂组分是通过将各成分简单地混合,例如在混合容器中轻微搅拌下混合,而容易地配制的。
这样的SCCO2基组合物一旦配制好就被施加到晶片表面,从而与其上的离子注入光致抗蚀剂接触,接触在合适的升高的压力下进行,例如在加压的接触室中,SCCO2基组合物以合适的体积流速和流量供给到接触室,以实现期望的接触作用来去除晶片表面的离子注入光致抗蚀剂。
应当理解,对于本发明的SCCO2基组合物,具体的接触条件可以在现有技术的范围内根据本文的描述而很容易地确定,而且在实现离子注入光致抗蚀剂从晶片表面理想去除的同时,本发明的SCCO2基组合物中各成分的具体比例和浓度可以宽泛地变化。
通过下文描述的说明性实施例可更全面展示本发明的特征和优点。
本研究中考察的晶片样品是Si/SiO2图案化晶片,其上具有深紫外线高剂量离子注入光致抗蚀剂层。将各种如本文所述的化学添加剂添加到SCCO2基组合物中,并评价光致抗蚀剂的去除效率。在整个去除实验中该SCCO2基组合物的温度被保持在70℃。上述层去除后,用大量的SCCO2/IPA和纯SCCO2彻底漂洗晶片以去除任何残留的溶剂和/或沉淀的化学添加剂。结果显示在图1-2中,如下面所述。
作为特定实施例,图1是控制晶片的光学显微镜图像,所述控制晶片上具有深紫外线(DUV)高剂量离子注入的光致抗蚀剂。
图2是对应清洗后样品的光学图像,通过在70℃、3000psi将所述含光致抗蚀剂的基片与SCCO2/IPA/甲酸清洗组合物接触而使所述光致抗蚀剂被清洗。从图2可观察到,在上述条件下光致抗蚀剂被完全除去。可以断定醇加上还原剂对去除高剂量离子注入光致抗蚀剂是有效的。
于是,上述照片证明了根据本发明的SCCO2基组合物用于从晶片表面去除离子注入光致抗蚀剂的有效性。
下面的配方实现了从图案化的Si/SiO2表面基本去除离子注入光致抗蚀剂。“基本去除”定义为由光学显微法确定的光致抗蚀剂从半导体器件大于约98%的去除。在这个具体的实施方式中,70℃、3000psi下经9分钟内,在所有的区域中都观察到离子注入光致抗蚀剂的100%去除。
组分 | 重量% |
甲酸(96%) | 0.60 |
异丙醇 | 6.0 |
SCCO2 | 93.4 |
据此,本文中已经就本发明的具体方面、特征和说明性的实施例对本发明进行了描述,但应当理解本发明的用途并不因此被限定,而是延伸为包括多个其他的方面、特征和实施方式。因此,下面提出的权利要求意在被广义地理解为包括这些方面、特征和实施方式,不超出其主旨和范围。
Claims (27)
1.离子注入光致抗蚀剂去除组合物,其包括至少一种超临界流体(SCF)、至少一种共溶剂和至少一种还原剂。
2.权利要求1的去除组合物,其中SCF包括选自二氧化碳、氧、氩、氪、氙和氨的流体。
3.权利要求1的去除组合物,其中SCF包括二氧化碳。
4.权利要求1的去除组合物,其中共溶剂包括至少一种C1-C6醇。
5.权利要求1的去除组合物,其中共溶剂包括异丙醇(IPA)。
6.权利要求1的去除组合物,其中还原剂包括如下的至少一种:甲酸、氢气、甲醛、福尔马林、硼烷、乙硼烷、胺稳定化的硼烷、胺稳定化的铝烷、和BH4与A1H4的四烷基胺。
7.权利要求6的去除组合物,其中还原剂包括甲酸。
8.权利要求1的去除组合物,其中SCF基去除组合物基于该组合物总重包括约60.0-约90.0重量%SCF、约10.0-约30.0重量%共溶剂和约0.01-约5.0重量%还原剂。
9.权利要求8的去除组合物,其中SCF包括二氧化碳。
10.权利要求8的去除组合物,其中共溶剂包括至少一种C1-C6烷醇。
11.权利要求8的去除组合物,其中还原剂包括如下的至少一种:甲酸、氢气、甲醛、福尔马林、硼烷、乙硼烷、胺稳定化的硼烷、胺稳定化的铝烷、和BH4与AlH4的四烷基胺。
12.从具有离子注入光致抗蚀剂的基片去除所述光致抗蚀剂的方法,所述方法包括在充分接触条件下,使具有离子注入光致抗蚀剂的基片与SCF基组合物接触充分长时间,从而将离子注入光致抗蚀剂从基片除去,所述SCF基组合物包括至少一种SCF、至少一种共溶剂和至少一种还原剂。
13.权利要求12的方法,其中SCF包括选自二氧化碳、氧、氩、氪、氙和氨的流体。
14.权利要求12的方法,其中SCF包括二氧化碳。
15.权利要求12的方法,其中接触条件包括约1500psi至约4500psi范围的压力。
16.权利要求12的方法,其中所述接触时间范围为约1分钟至约20分钟。
17.权利要求12的方法,其中共溶剂包括至少一种C1-C6醇。
18.权利要求12的方法,其中共溶剂包括异丙醇(IPA)。
19.权利要求12的方法,其中还原剂包括如下的至少一种:甲酸、氢气、甲醛、福尔马林、硼烷、乙硼烷、胺稳定化的硼烷、胺稳定化的铝烷、和BH4与AlH4的四烷基胺。
20.权利要求12的方法,其中还原剂包括甲酸。
21.权利要求12的方法,其中SCF基组合物基于该组合物总重包括约60.0-约90.0重量%SCF、约10.0-约30.0重量%共溶剂和约0.01-约5.0重量%还原剂。
22.权利要求12的方法,其中接触步骤包含循环,所述循环包括(i)SCF基组合物与具有离子注入光致抗蚀剂的基片的动态流动接触,和(ii)SCF基组合物与具有离子注入光致抗蚀剂的基片的静态浸泡接触。
23.权利要求22的方法,其中所述循环包括对具有离子注入光致抗蚀剂的基片交替、重复地进行动态流动接触(i)和静态浸泡接触(ii)。
24.权利要求12的方法,其进一步包括在第一洗涤步骤中用SCF/异丙醇水洗涤溶液、和在第二洗涤步骤中用SCF对已除去离子注入光致抗蚀剂的基片区域进行洗涤,从而在所述第一洗涤步骤中除去沉淀的残留化学添加剂,并在所述第二洗涤步骤中除去沉淀的残留化学添加剂和/或残留的醇。
25.权利要求24的方法,其中SCF包括SCCO2。
26.权利要求12的方法,其中接触条件包括约50℃-约90℃范围内的温度。
27.权利要求12的方法,其中光致抗蚀剂被置于高剂量离子注入处理,其中高剂量离子注入率高于1×1015原子/cm2。
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US10/827,395 US7557073B2 (en) | 2001-12-31 | 2004-04-19 | Non-fluoride containing supercritical fluid composition for removal of ion-implant photoresist |
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- 2005-04-12 CN CNA2005800118498A patent/CN101098954A/zh active Pending
- 2005-04-12 WO PCT/US2005/012301 patent/WO2005104682A2/en active Application Filing
- 2005-04-12 EP EP05734797A patent/EP1749087A2/en not_active Withdrawn
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KR20060135037A (ko) | 2006-12-28 |
EP1749087A2 (en) | 2007-02-07 |
WO2005104682A2 (en) | 2005-11-10 |
JP2007535697A (ja) | 2007-12-06 |
WO2005104682A3 (en) | 2007-02-01 |
US7557073B2 (en) | 2009-07-07 |
TW200609347A (en) | 2006-03-16 |
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