CN101959977A - 微电子基底清洁组合物 - Google Patents
微电子基底清洁组合物 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/34—Organic compounds containing sulfur
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31127—Etching organic layers
- H01L21/31133—Etching organic layers by chemical means
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
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- Oil, Petroleum & Natural Gas (AREA)
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- Organic Chemistry (AREA)
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- Cleaning Or Drying Semiconductors (AREA)
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Abstract
微电子清洁组合物，其包含：a)该组合物约80％至约99％重量的至少一种有机砜；b)该组合物约0.5％至约19％重量的水；和c)该组合物约0.5％至约10％重量的至少一种提供四氟硼酸根离子的组分，和d)任选至少一种多元醇。其尤其用于从具有Si基抗反射涂层和低k电介质的微电子基底或设备清洁蚀刻/灰化残余物。
Description
技术领域
本发明涉及组合物，其用于通过去除等离子蚀刻后或蚀刻/灰化后残余物清洁微电子基底以及硅基抗反射涂层，且能够在与铝、铜和低k电介质，且特别是多孔低k电介质相容的情况下进行清洁。特别地，本发明提供基本上基于溶剂的去除剂组合物，且还提供使用该组合物清洁微电子基底和设备的方法。
背景技术
半导体设备已通过以下步骤而制备：用光致抗蚀剂涂覆无机基底；通过暴露于光且随后显影而使光致抗蚀剂膜形成图案；使用该形成图案的光致抗蚀剂膜作为掩模蚀刻该无机基底的暴露区域以形成微小电路；和从无机基底去除该形成图案的光致抗蚀剂膜。或者，以上述相同方式形成微小电路后，将该形成图案的光致抗蚀剂膜灰化，然后将剩余的抗蚀剂残余物从无机基底去除。
随着更小电路线的进步，以及使用更先进的光刻术(例如，193nm，ArF)获得该电路线，需要抗反射涂层以控制临界尺寸(CD)和保持高图象质量。因此，最近扩大了Si基旋压(spin-on)抗反射涂层的作用以加入图像转移职责。使用该旋压Si基抗反射涂层的优点通常至少为双重的：它们易于平面化，且与使用ArF在193nm的光刻术所需的光致抗蚀剂的化学组成差别足够大，以使得促进了干法刻蚀过程中高分辨图像转移。然而，在干法刻蚀步骤之后，需要去除任何光致抗蚀剂或光致抗蚀剂残余物和剩余的抗反射涂层，而不损坏下面的电介质层或任何已进行的金属化。
因此需要提供去除蚀刻/灰化残余物、光致抗蚀剂和抗反射涂层的清洁组合物，且同时不损坏任何下面的电介质层或微电子设备的金属化(metallization)。特别需要提供用于去除蚀刻/灰化残余物、光致抗蚀剂和Si-抗反射涂层的清洁组合物，同时不损坏任何潜在的低k电介质层，特别是任何多孔低k电介质层，它们本身为化学类似的材料，且不损坏任何微电子设备的金属化，特别是铜或铝金属化。
发明内容
本发明的去除残余物的清洁组合物为基于含酸性四氟硼酸根的溶剂的组合物。这些组合物具有的pH为3或更小，且包含约80％至约99％重量的砜溶剂，约0.25％至19％重量水，约0.25％至10％重量的至少一种提供四氟硼酸根离子(BF4 -)的组分。该组合物可包含螯合剂，多元醇，表面活性剂和酸。本发明的组合物可用于清洁微电子基底以去除蚀刻/灰化残余物，特别是从包括含Si抗反射涂层以及下面的低k电介质层(特别是任何多孔低k电介质层)的那些微电子基底清洁。为实现清洁微电子基底或设备，该微电子基底或设备与本发明的组合物在足以实现该清洁的温度下接触足以实现该清洁的时间。
发明详述
本发明的去除残余物的清洁组合物为基于包含酸性四氟硼酸根的有机砜溶剂的组合物。这些组合物具有的pH为3或更小，且包含约80％至约99％重量的至少一种砜溶剂，约0.25％至约19％水和约0.25％至约10％重量的至少一种提供四氟硼酸根离子(BF4 -)的组分。
任何合适的有机砜可在本发明的组合物中使用。合适的砜包括，但不限于，二甲基砜，二乙基砜，二苯基砜，2-(甲基锍)乙醇，甲基苯基砜，乙基苯基砜，二丁基砜，二苄基砜和四氢噻吩-1，1-二氧化物(环丁砜)。优选环丁砜。本发明的清洁组合物中存在的砜组分的量的范围通常为该组合物的约80％至约99％重量，优选约85％至约95％，且更优选约89％至约93％。
本发明的清洁组合物中存在的水的量通常为该组合物的约0.25％至约19％重量，优选约2％至约14％，且更优选约4％至约10％。
提供四氟硼酸根离子的组分可为任何合适的可离子化的含四氟硼酸根的化合物，如，但不限于四氟硼酸HBF4，及其盐与强无机酸的组合。合适的盐包括，但不限于四氟硼酸铵(NH4BF4)，N-甲基-N-烷基吡咯烷鎓四氟硼酸盐，烷基四氟硼酸铵盐，碱金属四氟硼酸盐如锂、钠或钾四氟硼酸盐。任何合适的强无机酸可与四氟硼酸盐一起使用，且包括，但不限于，强无机酸如盐酸，硫酸，磷酸和硝酸。用于本发明的清洁组合物以提供四氟硼酸根离子优选为四氟硼酸，HBF4。四氟硼酸通常为商购的48％的水溶液，且可原样使用。四氟硼酸经历水解产生一些量的HF。组合物中HF的存在使得可选择性蚀刻Si基材料。提供四氟硼酸根离子的组分在本发明的清洁组合物中存在的量通常为该组合物的约0.25％至约10％重量，优选约1.5％至约7％，且更优选约2.5％至约4.5％。
本发明的清洁组合物的pH为pH 3或更小，优选pH约为2。本发明的清洁组合物的高酸性可通常归因于砜组分的特性。环丁砜为非质子溶剂，其在强酸的存在下不质子化。该特征使得相比于强无机酸水溶液，在低酸浓度下有非常高的酸性。
用备选Lewis碱溶剂，例如DMSO和乙二醇醚制备类似组合物的尝试是不成功的。上述制剂不具有去除Si基抗反射涂层的选择性，且它们也不保持与Cu的相容性。砜和BF3形成稳定的络合物。已报道四氟硼酸根离子(BF4 -)将离解为BF3和F-。在本发明中，认为砜-BF3络合物有助于将铜蚀刻速率减少为可接受的值。
本发明的清洁组合物可任选包含至少一种多元醇。如果本发明的清洁组合物中存在多元醇组分，其存在量可为清洁组合物的约1wt％至约10wt％，优选约2wt％至约8wt％，且更优选约3wt％至约6wt％。合适的多元醇包括，但不限于，乙二醇，甘油，赤藓醇，阿糖醇，木糖醇，甘露醇和山梨醇，且优选甘油。已证明(表X)使用多元醇的制剂具有增加的Cu相容性和光致抗蚀剂残余物去除能力。
相对于低k电介质，对抗反射涂层，本发明的清洁组合物能保持特别高(高达约70∶1)的蚀刻选择性，尽管它们本身是有些类似的材料。本发明的清洁组合物的pH为3或更小，其将上述蚀刻选择性赋予该清洁组合物，因为pH值大于3，清洁组合物将不可接受地蚀刻低k电介质材料。
本发明的清洁组合物可有效用于去除/清洁等离子刻蚀/灰化后残余物，金属基硬掩模和Si基抗反射涂层。本发明的组合物还具有铜和低k电介质相容性。本发明的一些组合物还具有铝相容性。
本发明的清洁组合物的理想的蚀刻速率选择性通过表1中对于Si基抗反射涂层、铜和铝金属化(metallization)和电介质(包括低k电介质)的蚀刻速率数据阐述。在该蚀刻实施例中，使用的本发明的清洁组合物包含3wt％HBF4，3.25wt％水和93.75wt％环丁砜。表中所列的材料用该清洁组合物在60℃处理10分钟，且观察到以下蚀刻速率。
表1
已对现有技术清洁组合物测试了是否它们在Si基抗反射涂层和电介质之间具有Si基蚀刻选择性。
美国专利申请公开号US 2006/0014656中实施例1的组合物相对Honeywell Duotm-193Si基抗反射涂层、铜和TEOS和Black Diamond 2电介质在50℃测试10分钟，且观察到的蚀刻速率(埃/分钟)如下。
表2
| CU | TEOS | DUOTM193 | Black Diamond 2 |
| ＜1 | ＞100 | ＞140. | ＞250 |
该现有技术制剂将以良好蚀刻速率蚀刻和去除Si基抗反射涂层，但也会不可接受地蚀刻低k Black Diamond电介质。
美国专利申请公开号US 2006/199749的表4中实施例23的组合物相对Honeywell Duotm-193Si基抗反射涂层、铜和TEOS和Black Diamond 2电介质在25℃和35℃测试10分钟，且观察到的蚀刻速率(埃/分钟)如下。
表3
| 温度℃ | Cu | TEOS | DUOtm-193 | Black Diamond 2 |
| 25℃ | 1 | 3 | 1 | 31 |
| 35℃ | 2 | 3 | 5 | 1 |
该基于主要含水和乙二醇醚(glycolic ether)酸性氟化物的制剂不能从基底去除Si基抗反射材料。
本发明的清洁组合物具有砜溶剂作为溶剂的关键性以及在该清洁组合物中避免存在乙二醇醚的必要性通过以下测试证实。制备以下三种清洁组合物。组合物A(本发明)包含92.7％环丁砜，3.8％水和3.5％四氟硼酸。在对比组合物B中，一部分环丁砜用卡必醇(二甘醇单甲基醚)代替，且在对比组合物C中，环丁砜完全被卡必醇代替。这些组合物的每一种相对Honeywell Duotm-193 Si基抗反射涂层、铜和TEOS和Black Diamond 2电介质在60℃测试30分钟。蚀刻结果(埃/分钟)如下。
表4
| 组合物 | Cu | TEOS | DUOTM-193 | Black Diamond 2 |
| A | ＜3 | 3 | ＞140 | ＜2 |
| B | 18 | 2 | 43 | 0 |
| C | 300 | 3 | 41 | 0 |
当与Cu相比，在本发明的组合物中部分或完全加入乙二醇醚破坏了Si基抗反射涂层的选择性蚀刻。
本发明的清洁组合物的理想的蚀刻速率选择性通过表1中对于Si基抗反射涂层、DUOTM-193、铜和铝金属化和电介质(包括低k电介质)的蚀刻速率数据阐述。所有化学品按供应商提供的使用。该研究在使用的HBF4为48％重量水溶液。所有蚀刻速率(埃/分钟)在60℃测定。处理Cu、Al和Black Diamond 2(BD2)的基底30分钟。DUOTM处理10分钟(初始厚度为约1400埃)。pH测量从组合物的10％重量水溶液确定。CuOx的去除基于可视检查Cu涂覆的晶片而判断，该晶片浸没在30％H2O2中约30分钟，然后用以下所列的组合物进行1分钟的处理。
表5
*螯合剂的量为约0.25％重量：DTPA＝二亚乙基三胺五乙酸，EDTA＝乙二胺四乙酸，且CyDTA＝1，2-二氨基环己烷-N，N，N′，N′-四乙酸；
BD2＝Applied Material，Inc.的Black Diamond 2-低K电介质
尽管本发明已参考其具体实施方案进行了描述，应理解可进行改变、修饰和变化而不偏离本文公开的发明构思的精神和范围。因此，预期其包括落入所附权利要求的精神和范围内的所有这些改变、修饰和变化。
Claims (16)
1.微电子基底清洁组合物，其包含：
a)该组合物约80％至约99％重量的至少一种有机砜；
b)该组合物约0.25％至约19％重量的水；和
c)该组合物约0.25％至约10％重量的至少一种提供四氟硼酸根离子的组分
其中该组合物作为10％重量水溶液的pH为3或更小。
2.根据权利要求1的微电子基底清洁组合物，还包含约1％至约10％重量的至少一种多元醇。
3.根据权利要求1的微电子基底清洁组合物，其中所述砜包括环丁砜。
4.根据权利要求1的微电子基底清洁组合物，其中所述至少一种提供四氟硼酸根离子的组分包括四氟硼酸。
5.根据权利要求3的微电子基底清洁组合物，其中所述至少一种提供四氟硼酸根离子的组分包括四氟硼酸。
6.根据权利要求2的微电子基底清洁组合物，其中至少一种多元醇包括甘油。
7.根据权利要求6的微电子基底清洁组合物，其中所述至少一种砜包括环丁砜，且所述至少一种提供四氟硼酸根离子的组分包括四氟硼酸。
8.清洁微电子基底或设备的蚀刻/灰化后残余物的方法，其包括将微电子基底或设备与清洁组合物接触，该清洁组合物包含：
a)该组合物约80％至约99％重量的至少一种有机砜；
b)该组合物约0.25％至约19％重量的水；和
c)该组合物约0.25％至约10％重量的至少一种提供四氟硼酸根离子的组分
其中该组合物作为10％重量水溶液的pH为3或更小。
9.根据权利要求8的方法，其中该清洁组合物还包含约1％至约10％重量的至少一种多元醇。
10.根据权利要求8的方法，其中所述砜包括环丁砜。
11.根据权利要求8的方法，其中所述至少一种提供四氟硼酸根离子的组分包括四氟硼酸。
12.根据权利要求10的方法，其中所述至少一种提供四氟硼酸根离子的组分包括四氟硼酸。
13.根据权利要求9的方法，其中至少一种多元醇包括甘油。
14.根据权利要求13的方法，其中所述至少一种砜包括环丁砜，且所述至少一种提供四氟硼酸根离子的组分包括四氟硼酸。
15.根据权利要求8的方法，其中所述微电子基底或设备包括Si基抗反射涂层和低k电介质。
16.根据权利要求14的方法，其中所述微电子基底或设备包括Si基抗反射涂层和低k电介质。
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| CN1659480A (zh) * | 2002-06-07 | 2005-08-24 | 马林克罗特贝克公司 | 用于微电子基底的清洁组合物 |
| WO2006065256A1 (en) * | 2004-12-10 | 2006-06-22 | Mallinckrodt Baker, Inc. | Non-aqueous, non-corrosive microelectronic cleaning compositions containing polymeric corrosion inhibitors |
| WO2006107517A2 (en) * | 2005-04-04 | 2006-10-12 | Mallinckrodt Baker, Inc. | Composition for cleaning ion implanted photoresist in front end of line applications |
Also Published As
| Publication number | Publication date |
|---|---|
| US8168577B2 (en) | 2012-05-01 |
| EP2247672B1 (en) | 2013-06-05 |
| KR101570256B1 (ko) | 2015-11-18 |
| BRPI0908905A2 (pt) | 2015-09-22 |
| IL207605A0 (en) | 2010-12-30 |
| JP5512554B2 (ja) | 2014-06-04 |
| CA2716641A1 (en) | 2009-09-03 |
| JP2011516620A (ja) | 2011-05-26 |
| EP2247672A1 (en) | 2010-11-10 |
| WO2009108474A1 (en) | 2009-09-03 |
| ZA201005419B (en) | 2011-04-28 |
| CN101959977B (zh) | 2013-12-04 |
| TW200942608A (en) | 2009-10-16 |
| IL207605A (en) | 2014-02-27 |
| US20110046036A1 (en) | 2011-02-24 |
| KR20100125270A (ko) | 2010-11-30 |
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