CN1479780A - 蚀刻设备组件的清洗方法 - Google Patents
蚀刻设备组件的清洗方法 Download PDFInfo
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
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- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
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- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
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Abstract
本发明涉及一种用于从蚀刻设备组件上去除蚀刻残留物的方法。所用组合物为含水酸性组合物，其中含有氟化物和极性有机溶剂。该组合物不含乙二醇和羟胺，且表面张力和粘度都较低。
Description
背景技术
在半导体器件的制备中往往需要将各种材料从基底上去除。等离子蚀刻、活性离子蚀刻、离子抛光等方法正越来越多地被用于从基底上去除材料。在这些去除操作中会形成各种副产物。这些副产物是由等离子气体、基底和抗蚀材料相互反应的结果。这些副产物的形成还受到蚀刻设备的类型和处理条件的影响。这些蚀刻残留物除了重新沉积在基底上，还会在蚀刻设备的暴露表面上形成不希望的沉积。为了延长蚀刻设备的使用寿命，人们想出各种办法来去除蚀刻设备的暴露表面上的不希望的残留物。例如有一种方法包括使用小颗粒，如沙子或玻璃小球通过喷砂处理来去除蚀刻设备组件上的不希望的残留物。其他的方法需要将蚀刻设备组件浸泡在洗液中，美国专利No.5,334,332公开的方法就是一个例子。根据该专利文献，蚀刻设备组件被浸泡在一种含有羟胺、链烷醇胺、水和邻苯二酚的洗液中。
发明概述
本发明涉及一种去除蚀刻设备上的蚀刻残留物而又不损坏设备表面的方法。本发明方法所用组合物为水性，且不含羟胺。该水性组合物含有一种酸性缓冲溶液、一种可以任意比溶于水的极性有机溶剂和一种氟化物。所述组合物的pH值介于3到6之间。
发明详述
本发明涉及一种通过将蚀刻设备组件浸入水性洗液而去除蚀刻设备上形成的蚀刻残留物的方法，其中包括：
A.一种酸性缓冲溶液，
B.一种可以任意比溶于水的极性有机溶剂，和
C.一种氟化物。所述组合物的pH值介于3到6之间，且不含羟胺。
根据本发明，蚀刻设备组件被浸入一含有水性清洁组合物的洗液中。典型地，洗液温度保持在20℃至40℃之间。尽管温度高于40℃的洗液也可以使用，但水分的蒸发会缩短洗液的使用寿命。蚀刻设备组件在洗液中泡够规定的时间之后，将其取出，通过喷洗或浸泡将其彻底冲洗干净。通常3到5分钟便可以将洗液残留物彻底冲掉。蚀刻设备组件在惰性气体流中或通过加热干燥。可以选择性地使用声波(强声波或超声波)来搅动洗液。
本方法所用组合物优选含有足够量的酸性缓冲溶液以便将组合物的pH值保持在大约3到6之间；含有30重量％到90重量％的一种可以任意比溶于水的极性有机溶剂；含有0.1重量％到20重量％的氟化铵；含有0.5重量％到40重量％的水；和不高于15重量％的抗腐蚀剂。所有的重量比都基于水性洗液的总重量算得。
介于约3到9之间的pH值环境将使得大多数易腐蚀金属对轻微腐蚀表现出惰性。然而，在某些情况下，为了去除高度无机化的蚀刻残留物，可能会使用略显酸性的pH环境。本发明方法通过使用一种酸性缓冲溶液将所用的洗液组合物的pH范围调整在理想的范围。优选的缓冲溶液含有一种羧酸或多元酸的铵盐。此类铵盐的一个例子是醋酸铵或磷酸铵。特别优选的是由醋酸铵和醋酸形成的酸性水溶液。缓冲溶液的配制方法为本领域所公知。在水性洗液中加入酸性缓冲溶液使得洗液组合物能够缓冲pH的波动，并且使其不易于对那些用于蚀刻设备组件的易腐蚀的金属，例如铝造成腐蚀。本发明所用极性有机溶剂可以任意比溶于水。二甲基亚砜由于对健康不利，不是本发明的优选极性有机溶剂。可用于本发明的溶剂包括例如二甲基乙酰胺(DMAC)、二甲基吡咯烷酮(DMPD)、单乙醇胺、N-甲基乙醇胺、甲酰胺、N-甲基甲酰胺、N-甲基吡咯烷酮(NMP)以及类似化合物。优选DMAC。DMAC的使用会形成一种组合物，其表面张力小于30mN/m，粘度约为10厘泊。这将更易润湿和冲洗。
氟化物是洗液组合物中的一个重要成分。含氟组合物包括那些具有通式R1R2R3R4NF的化合物，其中R1、R2、R3和R4独立地为氢、醇基、烷氧基、烷基或者它们的混合。这样的组合物的例子包括氟化铵、氟化四甲基铵和氟化四乙基铵。还可以使用氟硼酸。优选氟化铵，可以商购获得该化合物的40％水溶液。
水可以其他组分的一部分的形式出现，例如在氟化铵水溶液中，也可以单独加入。在无机蚀刻残留物的去除中，水的加入改善了氟化铵在洗液和酸中的溶解度。
乙二醇和其它溶剂的加入将使得组合物在25℃下的表面张力大于40mN/m，而粘度也会高于40厘泊，这些溶剂不包括在本发明的洗液中。
可以在水性洗液中加入不高于15重量％的抗腐蚀剂。优选抗腐蚀剂的含量在0.5重量％到8重量％之间。本领域所熟知的抗腐蚀剂，如在此用作参考文献的美国专利No.5,417,877中所公开的抗腐蚀剂，均可使用。据发现，在pH值小于6的体系中，pKa大于6的抗腐蚀剂不如pKa小于6的抗腐蚀剂好用。因此，优选的抗腐蚀剂组合物是那些pKa小于6的抗腐蚀剂。优选的抗腐蚀剂包括(邻)氨基苯甲酸、没食子酸、苯甲酸、p-甲基苯磺酸、十二烷基苯磺酸、异酞酸、马来酸、富马酸、D，L-苹果酸、丙二酸，邻苯二甲酸、马来酸酐、邻苯二甲酸酐等。可用但非优选的抗腐蚀剂如邻苯二酚、焦酚、没食子酸的酯。
本发明用于去除蚀刻残留物的水性洗液对蚀刻设备组件无腐蚀，不易燃并且低毒。该水性洗液组合物在20℃下即可有效去除蚀刻残留物，并且由于其低的表面张力和粘度而易于从蚀刻设备组件上冲去。
本发明方法的实施是将带有以薄膜或残留物形式存在的有机或金属有机聚合物、无机盐、氧化物、氢氧化物或者这些成分的复合或混合物的蚀刻设备组件与所公开的水性洗液相接触。温度、时间等实际的条件取决于所要清除的蚀刻残余物的特点和厚度。一般而言，要除去蚀刻残余物，需要将设备组件浸入一个装有水性洗液的容器，洗液温度保持在约20℃到80℃，优选在约20℃到40℃，持续时间可以是7分钟，也可以超过二十四小时，决定于所要清除的蚀刻残余物的类型和沉积的量。
有了上面这些对本发明的描述，下面将通过实施例来进一步说明而不是限定本发明。在下面的实施例中，通过使用5％的水溶液在室温下确定pH值。表面张力和粘度的测量是在25℃下进行的。在室温下混合如下组分得到组合物。
实施例1组分 重量％DMAC 57.5水(去离子) 12.4氟化铵(40％水溶液) 2.5醋酸(冰醋酸) 12.0醋酸铵 15.6组合物的pH值为4.75。组合物表面张力为28mN/m，粘度为10厘泊。
实施例2组分 重量％NMP 57.5水(去离子) 12.4氟化铵(40％水溶液) 2.5醋酸(冰醋酸) 12.0醋酸铵 15.6组合物的pH值为4.75。组合物表面张力为42.2mN/m，粘度为12.0厘泊。
实施例3组分 重量％DMPD 57.5水(去离子) 12.4氟化铵(40％水溶液) 2.5醋酸(冰醋酸) 12.0醋酸铵 15.6组合物的pH值为4.75。组合物表面张力为31.5mN/m，粘度为18.0厘泊。
Claims (12)
1.一种用于从蚀刻设备组件上去除蚀刻残留物的方法，该方法包括：将蚀刻设备组件放入水性洗液中，该水性洗液含有：
A.一种酸性缓冲溶液，
B.一种可以任意比溶于水的极性有机溶剂，和
C.一种氟化物。
直至蚀刻残留物被清除，所述洗液的pH值保持在大约3到6之间，且不含羟胺。
2.权利要求1所述方法，其中水性洗液还包含一抗腐蚀剂。
3.权利要求1所述方法，其中酸性缓冲溶液含有羧酸或多元酸的铵盐。
4.权利要求1所述方法，其中极性有机溶剂为单乙醇胺、N-甲基乙醇胺、甲酰胺、N-甲基甲酰胺、二甲基乙酰胺(DMAC)、二甲基吡咯烷酮(DMPD)、N-甲基吡咯烷酮(N MP)或它们的混合物。
5.权利要求1所述方法，其中氟化物具有通式R1R2R3R4NF，其中R1、R2、R3和R4独立地为氢、醇基、烷氧基或烷基。
6.权利要求2所述方法，其中抗腐蚀剂的pKa小于6。
7.权利要求2所述方法，其中抗腐蚀剂为(邻)氨基苯甲酸、没食子酸、苯甲酸、p-甲基苯磺酸、十二烷基苯磺酸、马来酸、富马酸、D，L-苹果酸、异酞酸、丙二酸，邻苯二甲酸、马来酸酐、邻苯二甲酸酐，或它们的混合物。
8.权利要求3所述方法，其中酸性缓冲液为醋酸与醋酸铵的溶液。
9.权利要求1所述方法，其中氟化物为氟硼酸。
10.权利要求5所述方法，其中氟化物为氟化铵、氟化四甲基铵或氟化四乙基铵。
11.权利要求1所述方法，其中水性洗液的表面张力小于或等于30mN/m，粘度小于或等于15厘泊。
12.权利要求1所述方法，其中水性洗液被搅动。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/732,414 | 2000-12-07 | ||
| US09/732,414 US6656894B2 (en) | 2000-12-07 | 2000-12-07 | Method for cleaning etcher parts |
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| CN1266262C CN1266262C (zh) | 2006-07-26 |
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| US (1) | US6656894B2 (zh) |
| EP (1) | EP1341883A4 (zh) |
| KR (1) | KR20030070055A (zh) |
| CN (1) | CN1266262C (zh) |
| AU (1) | AU2002216661A1 (zh) |
| WO (1) | WO2002046344A1 (zh) |
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- 2001-12-03 AU AU2002216661A patent/AU2002216661A1/en not_active Abandoned
- 2001-12-03 EP EP01999625A patent/EP1341883A4/en not_active Withdrawn
- 2001-12-03 CN CNB018202985A patent/CN1266262C/zh not_active Expired - Fee Related
- 2001-12-03 KR KR10-2003-7007615A patent/KR20030070055A/ko not_active Application Discontinuation
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Also Published As
| Publication number | Publication date |
|---|---|
| US6656894B2 (en) | 2003-12-02 |
| US20020107158A1 (en) | 2002-08-08 |
| CN1266262C (zh) | 2006-07-26 |
| KR20030070055A (ko) | 2003-08-27 |
| EP1341883A4 (en) | 2004-06-02 |
| WO2002046344A1 (en) | 2002-06-13 |
| EP1341883A1 (en) | 2003-09-10 |
| AU2002216661A1 (en) | 2002-06-18 |
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