CN1124763A - 半导体晶片清洗剂及其清洗方法 - Google Patents
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Abstract
本发明涉及一种半导体晶片清洗剂及其清洗方法。本发明的含水清洗剂其pH值为1—5，优选为1—3，且含有至少一种表面活性剂和至少一种属于包括琥珀酸和其衍生物化合物在内的一组中的化合物。为了清洗半导体晶片，优选采用机械工具在半导体晶片的侧面产生清洗剂的薄膜。
Description
本发明涉及一种半导体晶片清洗剂及其清洗方法。清洗的目的是为了除去晶片表面的污染物。应当理解，术语污染物特别是指外来金属杂质、有机化合物和直径小于1微米的颗粒物。
人们早就已知并经常使用的清洗方法是所谓的RCA清洗法(W.Kern和D.A.Puotionen，RCA Review，vol.31，p187-206(1970))。该方法的基本组成是两个清洗池，其中，半导体晶片先用称为SC1溶液的含水液体处理，然后再用称为SC2溶液的含水液体进行处理，SC1溶液是一种含过氧化氢和氢氧化铵的溶液，其所具有的氧化性质和碱性能够除去颗粒物和有机残留物，SC2溶液是一种以稀盐酸和过氧化氢为基础的溶液，用此溶液可以除去经过处理的半导体晶片表面上的大部分外来金属杂质。这种两步RCA清洗法的缺点是，虽然SC1溶液能够基本上除去半导体晶片表面的颗粒物，但却同时又给其带来了另外的外来金属杂质污染源如铁、锌和铝。尽管通过后一步SC2溶液处理有可能明显地降低晶片表面上外来金属杂质的可测浓度，但该处理的结果是使粘附在晶片表面上的颗粒物数量再次增加(P.H.Singer in Semiconductor Internationa1，P36-39(1992年12月))。
在各种不同的半导体晶片清洗方法中，将能量以声波形式(“强声(megasonic)或超声清洗”)(或动能形式(“洗涤器方法(scrubber method)”))引入含有半导体晶片的清洗池中将有助于除去污染物。在所谓的“洗涤器方法”中，例如通过在半导体晶片侧面上的一系列辊轮产生了能够非常有效的洗涤表面粘附颗粒的强力流动的清洗剂膜。(W.C.Krusell和D.I.Golland，Proc.Electrochem.Soc.，P23-32(1990))。
本发明的目的是提供一种半导体晶片清洗剂及其清洗方法，其中所说的清洗剂和清洗方法能够有效地除去半导体晶片表面的污染物。
本发明的目的是通过一种用于清洗半导体晶片的含水清洗剂实现的，其中所说的清洗剂含有至少一种表面活性剂和至少一种属于包括琥珀酸和其衍生物化合物在内的一组中的化合物，该清洗剂的pH值为1-5，优选为1-3。另外，本发明的目的是通过方法独立权利要求中的特征部分所述的方法实现的。
本发明的清洗剂和方法特别适用于清洗由硅组成的半导体晶片。
半导体晶片在其生产过程中必须反复清洗。一般来说，晶片表面的机械或化学处理的最后步骤都是清洗步骤。例如，在化学浸蚀后或抛光后正象精研后一样，有必要对晶片进行清洗。前述RCA清洗法一般是用于清洗抛光后的半导体晶片。原则上说，在半导体晶片生产过程中所必需的任何清洗步骤均可用本发明的清洗剂进行。但优选将本发明的清洗剂用于清洗抛光后的半导体晶片。如果抛光后的半导体晶片先用SC1溶液或SC1溶液和SC2溶液预处理，最后再用本发明的清洗剂清洗可以达到特别好的清洗效果。
为了达到清洗目的，可以将半导体晶片浸泡在清洗剂池中。但优选向清洗剂中提供动能以助于清洗半导体晶片。为此目的，更优选采用“洗涤器方法”或在清洗剂存在下，与晶片侧面平行地移动一个或一个以上的塑料质辊轮。如果织物能够使清洗剂如此分布使得能在该晶片的侧面上形成流动的薄膜，则无需对半导体晶片施加机械力的作用。
除水外，清洗剂含有至少一种表面活性剂和至少一种包括琥珀酸和其衍生物在内的一组中的化合物。此外，清洗剂的pH值为1-5，优选为1-3。清洗剂也可含或不含盐酸。盐酸可以用来，例如调节清洗剂的pH值。
清洗剂中的表面活性剂成分优选占0.01-1％(重量)。特别优选的是含有0.01-0.1％(重量)表面活性剂的清洗剂。作为表面活性剂，可以使用单一化合物也可以使用表面活性剂的混合物。优选在水溶液中可以产生中性或微酸性pH值的阴离子型表面活性剂、两性表面活性剂或非离子型表面活性剂。特别优选的表面活性剂是乙氧基化烷基酚和烷基聚乙二醇醚硫酸盐。
所说的清洗剂含有一种或一种以上属于包括琥珀酸和其衍生物的化合物在内的一组中的化合物。该组中特别值得一提的化合物是琥珀酸、磺基琥珀酸以及它们的一酯和二酯衍生物。琥珀酸(HOOCCH2CH2COOH)和/或磺基琥珀酸(HOOCCH2CH(SO3H)COOH)是特别优选的。该成分在清洗剂中的浓度优选总计0.001-1.0％(重量)，更优选为0.01-0.1％(重量)。
清洗剂中还可以选择性地含有具有金属配合特性的物质成分。羊毛铬黑T和/或铁蛋白特别适合于此目的。
下面通过实施例进行比较来证明本发明清洗剂的效果。
首先将50块经过抛光的、直径为150毫米的硅晶片进行标准RCA清洗。然后对其中的一半硅片检验其表面上的污染物(对比例1和2)，另一半硅片用本发明的清洗剂作最后的清洗处理。实施例1的含水清洗剂含有0.05％(重量)的壬基酚/环氧乙烷加成化合物和0.05％(重量)的磺基琥珀酸，并已用浓盐酸(0.01％(重量))将pH值调至2。实施例2的含水清洗剂的p H值为2，含有0.03％(重量)的壬基酚/环氧乙烷加成化合物和0.5％(重量)的磺基琥珀酸，但不含盐酸。
硅晶片的最后清洗处理是通过标准“洗涤器方法”进行的。然后，同样测定这些硅晶片的污染物残留量(实施例1和2)。
利用工业用计数器分析颗粒。用此仪器对颗粒进行计数，并按它们的平均直径分成三种类型。硅晶片表面上的外来金属杂质用VPD/TXRF测定法(蒸气相分解/总反射X-射线荧光)检测，但金属钠和铝是用VPD/AAS(蒸气相分解/原子吸收光谱)测定的。
测定结果总汇于下表中：a)颗粒测定：
0.1微米*) 0.2微米*) 0.3微米*)对比例1 564**) 79**) 6.2**)实施例1 525**) 72**) 4.2**对比例2 40** 5** 4.0**实施例2 40** 4.0**) 4.0**)*)粒径分为三个范围：＜0.1微米；0.1-＜0.2微米；0.2-0.3微米**)每块晶片上所发现的平均颗粒数。
b)外来金属杂质的测定***)：
K Ca Fe Ni对比例1 1*109 1*109 1*109 1*109实施例1 ＜1*108 ＜1*108 ＜1*108 ＜1*108对比例2****) ＜1*1010 1*1010 3*109 ＜1*109实施例2****) ＜1*1010 ＜8.5*109 ＜1*109 ＜1*109
Cu Zn Al Na对比例1 3*109 4*109 8*1010 3*1010实施例1 ＜1*108 3*108 2*1010 ＜2.2*1010对比例2****) 8*109 1*1010 2.5*1010 2.4*1010实施例2****) 6*109 ＜1*109 ＜1.4*1010 ＜3*1010***)所有数据的单位均为[原子/厘米2]，且为对晶片所做的一组试验测定结果的算术平均值。****)与对比例1和实施例1相比，与改进设备相关的检测限定。
Claims (8)
1、一种用于清洗半导体晶片的含水清洗剂，其中所说的清洗剂含有至少一种表面活性剂和至少一种属于包括琥珀酸和其衍生物化合物在内的一组中的化合物，该清洗剂的pH值为1-5，优选为1-3。
2、根据权利要求1所述的清洗剂，其中所述的清洗剂中表面活性剂成分的用量为0.01-1％(重量)，优选为0.01-0.1％(重量)。
3、根据权利要求1或2所述的清洗剂，其中所述的清洗剂含有琥珀酸和/或磺基琥珀酸。
4、根据权利要求1-3所述的清洗剂，其中所述的清洗剂还含有盐酸。
5、一种清洗半导体晶片的方法，该方法包括在半导体晶片的侧面产生含水清洗剂薄膜，所述的清洗剂含有至少一种表面活性剂和至少一种属于包括琥珀酸和其衍生物化合物在内的一组中的化合物，该清洗剂的pH值为1-5，优选为1-3。
6、根据权利要求5所述的方法，其中所述的薄膜是借助于机械工具产生的。
7、根据权利要求5或6所述的方法，其中所述的清洗剂含有琥珀酸和/或磺基琥珀酸。
8、根据权利要求5-7所述的方法，其中所述的清洗剂还含有盐酸。
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| DE4430217A DE4430217A1 (de) | 1994-08-25 | 1994-08-25 | Reinigungsmittel und Verfahren zum Reinigen von Halbleiterscheiben |
| DEP4430217.7 | 1994-08-25 | ||
| DE19515024.4 | 1995-04-24 | ||
| DE19515024A DE19515024A1 (de) | 1995-04-24 | 1995-04-24 | Reinigungsmittel und Verfahren zum Reinigen von Halbleiterscheiben |
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Cited By (3)
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|---|---|---|---|---|
| CN100423190C (zh) * | 2005-08-10 | 2008-10-01 | 株式会社上睦可 | 硅晶片的洗涤方法 |
| CN103013711A (zh) * | 2013-01-15 | 2013-04-03 | 常州比太科技有限公司 | 一种去除晶体硅片金属离子污染的清洗液及其清洗工艺 |
| CN103882444A (zh) * | 2012-12-19 | 2014-06-25 | 安集微电子（上海）有限公司 | 一种清洗液及其应用 |
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-
1995
- 1995-08-10 US US08/513,271 patent/US5695572A/en not_active Expired - Fee Related
- 1995-08-12 TW TW084108422A patent/TW330211B/zh active
- 1995-08-23 FI FI953947A patent/FI953947A/fi unknown
- 1995-08-24 DE DE59506147T patent/DE59506147D1/de not_active Expired - Fee Related
- 1995-08-24 EP EP95113289A patent/EP0698917B1/de not_active Expired - Lifetime
- 1995-08-24 KR KR1019950026371A patent/KR0157702B1/ko not_active IP Right Cessation
- 1995-08-25 JP JP7238995A patent/JP2709452B2/ja not_active Expired - Lifetime
- 1995-08-25 CN CN95115577A patent/CN1057330C/zh not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100423190C (zh) * | 2005-08-10 | 2008-10-01 | 株式会社上睦可 | 硅晶片的洗涤方法 |
| CN103882444A (zh) * | 2012-12-19 | 2014-06-25 | 安集微电子（上海）有限公司 | 一种清洗液及其应用 |
| CN103013711A (zh) * | 2013-01-15 | 2013-04-03 | 常州比太科技有限公司 | 一种去除晶体硅片金属离子污染的清洗液及其清洗工艺 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1057330C (zh) | 2000-10-11 |
| JP2709452B2 (ja) | 1998-02-04 |
| FI953947A (fi) | 1996-02-26 |
| FI953947A0 (fi) | 1995-08-23 |
| EP0698917B1 (de) | 1999-06-09 |
| KR0157702B1 (en) | 1998-12-01 |
| KR960009041A (ko) | 1996-03-22 |
| EP0698917A1 (de) | 1996-02-28 |
| TW330211B (en) | 1998-04-21 |
| US5695572A (en) | 1997-12-09 |
| DE59506147D1 (de) | 1999-07-15 |
| JPH08100195A (ja) | 1996-04-16 |
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