CN101337227A - 使用清洁溶液清洁半导体晶片的方法 - Google Patents
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Abstract
本发明涉及一种使用包含初始组成的铵碱性组分的清洁溶液清洁半导体晶片的方法，其中使所述半导体晶片以单晶片处理与清洁溶液接触，在清洁的过程中加入了氟化氢，以作为所述清洁溶液的其它组分，并且所述清洁溶液在清洁结束时具有不同于初始组成的组成。
Description
技术领域
本发明涉及使用清洁溶液清洁半导体晶片的方法，更准确地说，涉及一种其中所述半导体晶片按照单晶片处理模式进行清洁的方法。
背景技术
单晶片清洁方法相对于其中多个晶片同时进行清洁的多晶片清洁方法具有某些优点。这些优点包括低的化学品消耗、高的工艺灵活性以及使用不同的清洁溶液处理晶片前侧和晶片后侧的可能性。单晶片清洁方法的特别的优点在于排出了交叉污染、即污染物在半导体晶片之间转移的危险性。而这些方法的本质缺点在于，与多晶片处理相比其生产能力较低。但是，由于具有非常大直径(300rnm)的硅晶片在半导体工业中正日益得到处理，所以该缺点变得不再重要。单晶片清洁可以按照两种根本不同的方法进行。此时，清洁溶液可以以浴器提供，将半导体晶片浸渍到浴器中一段时间。更通常的情况是使用备选的设置，其中半导体晶片被锚定(anchor)在旋转的板上，清洁溶液通过喷嘴被注射或喷洒到所述半导体晶片的一个或两个外侧面上。用过的清洁溶液在离心力的作用下从所述半导体晶片流开。例如，这种单晶片处理的一个实例被描述在US 2004/0031503 A1中，其也适合于蚀刻半导体晶片。
尤其是其上面将要外延沉积一个或多个其它层的半导体晶片在沉积前必须要具有特别彻底清洁的表面。必须要除去的污染物是颗粒污染物、结合在表面上的金属离子、以及经常以表面薄膜的形式覆盖半导体晶片的有机化合物。氨和过氧化氢在水中的碱性溶液(氨过氧化物混合物APM)通常被用于除掉颗粒和有机化合物。高质量外延层沉积的重要的先决条件是，完全除去覆盖半导体材料如硅、锗、以及硅/锗合金表面的无定型氧化物层。表面氧化物使用含氟化氢HF的水溶液溶解。使用HF溶液处理过的半导体晶片具有疏水性的不含氧的表面。由于其对二氧化硅的高蚀刻速率而特别适合于此目的的清洁溶液包含氟化铵NH4F或四烷基氟化铵如四甲基氟化铵N(CH3)4F与氟化氢的混合物。WO 98/56726 A1显示，有利的是，直到直接使用前再由氢氧化铵或氢氧化四烷基铵与氟化氢来制备所述的清洁溶液。
发明内容
本发明的目的是提供一种清洁方法，该方法具有优于和高于单晶片处理、以及在其使用场所制备清洁溶液的优点的改进的清洁效果。
本发明涉及一种使用包含初始组成的铵碱性组分的清洁溶液清洁半导体晶片的方法，其中使所述半导体晶片按照单晶片处理与清洁溶液接触，在清洁的过程中加入氟化氢以作为所述清洁溶液的其它组分，并且所述清洁溶液在清洁结束时具有不同于初始组成的组成。
具体实施方式
本方法的特点在于，清洁溶液的组成在清洁过程中变化，以便以目标方式控制清洁机理。在清洁开始时，所述清洁溶液含有铵碱性组分，但是不含HF。在清洁的过程中，氟化氢被加入以作为清洁溶液的其它组分。由此实现了首先产生的条件最适于将颗粒从半导体晶片溶解，并将其永久地转移至清洁溶液中，而后面建立的条件最适于永久地从半导体晶片除去金属，并将表面上的氧化物薄膜彻底剥离掉。与使用固定预设定组成的清洁溶液相比，全面的效果是具有改进的清洁效果，即使该清洁溶液也是如在本发明的方法中直到使用时才制备一样。
对清洁溶液浓度的变化进行控制，以使氟化氢与铵碱性组分的摩尔浓度之比HF∶NR4OH在开始清洁时为＜1，至清洁结束时为＞1。R表示H或C1-4的烷基，其中四甲基氢氧化铵(N(CH3)4OH，TMAH)相对于氢氧化铵(NH4OH)和长链的四烷基氢氧化铵为优选。所述铵碱性组分在清洁溶液中的浓度在清洁开始时优选为0.001-25重量％，在结束时优选为0.001-10重量％。HF在清洁溶液中的浓度在清洁结束时优选为0.01-25重量％。HF∶NR4OH的摩尔数量之比在清洁结束时优选为1.1-100。随着氟化氢在清洁溶液中比例的增加，所述清洁溶液的pH下降，并且从强碱性范围的pH变化至pH为1-5的酸性范围。颗粒的清洁主要在碱性范围内，而金属的清洁主要在酸性范围内。由于在清洁过程结束时氟化氢相对于铵碱性组分过量，由此产生了溶解半导体晶片上的表面氧化物的溶液。铵离子吸附从半导体晶片剥离下来的颗粒，由此防止半导体晶片在进一步的清洁过程中的再污染。
在所述方法的优选构架中，半导体晶片首先与含TMAH、但不含HF的清洁溶液接触。这发生在适于进行单晶片处理的设备中，例如在具有溢流的浴器中，或在离心机中。直到进一步的清洁过程才向清洁溶液中加入氟化氢，其中HF是在一个或数个步骤中加入，或者是连续加入的。在浴器中进行清洁的情况下，开始时提供含有TMAH的水溶液，然后将半导体晶片浸渍到其中。其后通过在半导体晶片的存在下同时进一步将TMAH溶液和HF水溶液引入所述浴器中，从而在所述浴器中制备具有变化的组成的清洁溶液。如果合适，在进一步的清洁过程中将TMAH和HF的浓度和流入速度设定为彼此独立并且变化。这样，清洁溶液中HF的浓度可以另外仅通过相比于TMAH溶液流入速度的HF溶液流入速度的增加而增加，或相反，通过相比于HF流入速度的TMAH溶液流入速度的降低而增加。相应的情况发生在半导体晶片在离心机的板上进行清洁的过程中。首先，含有TMAH、并通过一个或数个喷嘴提供的水溶液被喷射或喷洒到在所述板上旋转的半导体晶片的一个或两个侧面上。其后，通过额外地经一个或数个其它喷嘴提供HF水溶液给半导体晶片，来制备在半导体晶片上具有改变的组成的清洁溶液。在本发明的该优选实施方案中，如果适宜，在其它的清洁过程中TMAH溶液和HF溶液的浓度也设定为彼此独立并变化。
还不含HF的清洁溶液的清洁阶段的优选周期是1-300秒，特别优选5-30秒。TMAH在所述清洁溶液中的浓度优选是在水中的0.001-25重量％。为了进一步改进移除颗粒的性能，所述清洁溶液在此阶段尤其可以含有表面活性剂和短链醇。适宜的表面活性剂尤其是阴离子和非离子的清洁剂，例如脂肪醇乙氧基化物、或长链的烷基磺酸盐。适宜的醇是例如丁醇、乙二醇或丙三醇。所述清洁溶液不应含有臭氧，过氧化氢或任何其它氧化剂。
其后提供的HF水溶液的浓度优选为在水中的0.01-50重量％。使用含有HF的清洁溶液清洁半导体晶片的清洁阶段的优选周期为1-300秒，特别优选5-30秒。
清洁溶液的温度在两个阶段是15-95℃，优选15-45℃。
在本发明方法结束时，半导体晶片的表面为疏水性的且不含表面氧化物。就进一步的处理而言，所述半导体晶片可以用另外的清洁溶液漂洗，如用去离子水，然后干燥。但是，也可以返回到所述方法的起点，并通过对所述半导体晶片使用具有初始组成的清洁溶液再次清洁而重复所述方法一次或多次。
具体来说，特别适于预先进行清洁处理的半导体晶片是具有由硅或硅和锗的合金构成的表面的半导体晶片，该表面将要被清洁以用于在其后进行涂敷。
Claims (8)
1.一种使用包含初始组成的铵碱性组分的清洁溶液清洁半导体晶片的方法，其中使所述半导体晶片以单晶片处理与所述清洁溶液接触，在清洁的过程中加入氟化氢作为所述清洁溶液的其它组分，并且所述清洁溶液在清洁结束时具有不同于初始组成的组成。
2.权利要求1的方法，其中氟化氢与铵碱性组分的摩尔浓度的比例HF：NR4OH在开始清洁时为＜1，到清洁结束时向上变化至＞1，其中R表示以下的基：H或甲基、乙基、丙基或丁基。
3.权利要求1或2的方法，其中氟化氢被加入所述清洁溶液中，并且所述铵碱性组分的浓度下降。
4.权利要求1-3之一的方法，其中所述清洁溶液含有表面活性剂或短链醇作为其它组分。
5.权利要求1-4之一的方法，其中所述清洁溶液不含臭氧或过氧化氢。
6.权利要求1-5之一的方法，其中所述清洁溶液被通过喷嘴注射或喷洒到旋转的半导体晶片上。
7.权利要求1-6之一的方法，其中所述清洁溶液被导入其中浸渍有所述半导体晶片的浴器中。
8.权利要求1-7之一的方法，其中所述清洁通过对半导体晶片使用初始组成的清洁溶液再次进行清洁来重复至少一次。
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| Application Number | Priority Date | Filing Date | Title |
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| DE102007030957.2 | 2007-07-04 | ||
| DE102007030957A DE102007030957A1 (de) | 2007-07-04 | 2007-07-04 | Verfahren zum Reinigen einer Halbleiterscheibe mit einer Reinigungslösung |
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| Publication Number | Publication Date |
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| CN101337227A true CN101337227A (zh) | 2009-01-07 |
| CN101337227B CN101337227B (zh) | 2011-11-16 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN200810108286XA Expired - Fee Related CN101337227B (zh) | 2007-07-04 | 2008-06-05 | 使用清洁溶液清洁半导体晶片的方法 |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US7938911B2 (zh) |
| JP (1) | JP4889691B2 (zh) |
| KR (1) | KR100992479B1 (zh) |
| CN (1) | CN101337227B (zh) |
| DE (1) | DE102007030957A1 (zh) |
| SG (1) | SG148967A1 (zh) |
| TW (1) | TWI388657B (zh) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102909204A (zh) * | 2011-08-05 | 2013-02-06 | 美新半导体（无锡）有限公司 | 清洗深硅刻蚀工艺后的圆片的方法 |
| CN102921656A (zh) * | 2011-08-10 | 2013-02-13 | 无锡华润上华科技有限公司 | 半导体晶圆的清洗装置及其清洗方法 |
| CN112216598A (zh) * | 2014-09-18 | 2021-01-12 | 台湾积体电路制造股份有限公司 | 用于半导体器件制造的清洁方法 |
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| SG170691A1 (en) | 2009-10-14 | 2011-05-30 | Rohm & Haas Elect Mat | Method of cleaning and micro-etching semiconductor wafers |
| CN102310060A (zh) * | 2011-07-07 | 2012-01-11 | 苏州赤诚洗净科技有限公司 | 太阳能电池硅片的清洗装置 |
| CA3085086C (en) | 2011-12-06 | 2023-08-08 | Delta Faucet Company | Ozone distribution in a faucet |
| JP2013187401A (ja) * | 2012-03-08 | 2013-09-19 | Dainippon Screen Mfg Co Ltd | 基板処理装置及び基板処理方法 |
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-
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- 2008-06-05 CN CN200810108286XA patent/CN101337227B/zh not_active Expired - Fee Related
- 2008-06-17 US US12/140,306 patent/US7938911B2/en not_active Expired - Fee Related
- 2008-06-24 SG SG200804774-8A patent/SG148967A1/en unknown
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102909204A (zh) * | 2011-08-05 | 2013-02-06 | 美新半导体（无锡）有限公司 | 清洗深硅刻蚀工艺后的圆片的方法 |
| CN102909204B (zh) * | 2011-08-05 | 2014-11-05 | 美新半导体（无锡）有限公司 | 清洗深硅刻蚀工艺后的圆片的方法 |
| CN102921656A (zh) * | 2011-08-10 | 2013-02-13 | 无锡华润上华科技有限公司 | 半导体晶圆的清洗装置及其清洗方法 |
| CN112216598A (zh) * | 2014-09-18 | 2021-01-12 | 台湾积体电路制造股份有限公司 | 用于半导体器件制造的清洁方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI388657B (zh) | 2013-03-11 |
| JP2009016833A (ja) | 2009-01-22 |
| JP4889691B2 (ja) | 2012-03-07 |
| SG148967A1 (en) | 2009-01-29 |
| CN101337227B (zh) | 2011-11-16 |
| KR20090004492A (ko) | 2009-01-12 |
| TW200902705A (en) | 2009-01-16 |
| US20090007940A1 (en) | 2009-01-08 |
| KR100992479B1 (ko) | 2010-11-08 |
| DE102007030957A1 (de) | 2009-01-08 |
| US7938911B2 (en) | 2011-05-10 |
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