CN1166051A - 从衬底表面除去碳的方法 - Google Patents
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Abstract
本发明是一种通过在分子氯和水蒸汽气氛加热从衬底上去除如碳、金属元素等材料的方法。在优选实施例中，从Si或GaAs衬底材料的表面去除碳残留物。
Description
本发明涉及从衬底表面除去碳的方法，特别是，本发明涉及一种用水蒸汽-氯气热清洁工艺除去衬底表面上的碳的方法。
制造半导体器件的通常方法中利用了已知为光刻胶的光敏聚合物。将光刻胶层旋涂于半导体衬底表面，其厚约1微米(10000Å)，并利用预先准备的光掩模进行构图曝光。然后象普通的照像技术那样显影。显影后，根据制造者的要求，从表面上除去未曝光区域，留下曝光或覆盖的所选晶片区域。这样便为下步工艺制备好了晶片，例如用硼离子轰击晶片表面，以将杂质原子引入硅晶片，改变其电特性。在该工艺步骤完成后，必须除去已显影的光刻胶区，以便利用不同的图形重复该过程。
目前半导体工业中标准的刻图和清洁方法所利用的液态化学溶液至少有自1970年以来就使用的称作“SPM”、“SC-1”和“SC-2”的三种。“SPM”代表的是“硫酸和过氧化物的混合物”，“SC”代表的是“标准清洗液”。SPM是浓硫酸和30％的双氧水的溶液，用于除去较重的有机物，例如光刻胶。SC-1是29wt/wt％的氢氧化氨、30％双氧水和去离子水的溶液。该溶液通常在约70℃-80℃的温度下使用，用以氧化有机膜的表面，去除某些金属离子。SC-2是由37wt/wt％的盐酸、30％的双氧水和去离子水构成的最后漂洗液，通常在约75-80℃温度下使用。这些溶液是在二十世纪六十年代由RCA公司首先研制出来的，有时就称它们为“RCA清洗液”。该方法可在低于100℃温度下进行，考虑到在处理过程中若任何时间温度达到约150-200℃则掺杂剂在晶片中的扩散失控，该方法是很有利的。
在主要考虑液体处理的安全性、环境问题和水的可用性时，这种液体处理工艺是不足的。另外，还存在来自这些材料的固有表面张力的更重要的局限。这些液体很难进入特征尺寸小于约0.3微米图形中。最后，因为液体处理工艺还需要干燥步骤以除去液态清洗剂，所以要花费较多工时，导致产量降低。由于器件和图形特征尺寸的不断减小，必须研究刻图和清洗的新方法。
解决有关液体清洗问题的最直接的方法是发展气相处理方法。气体较容易用体积较小的洗涤器处理，不需要干燥步骤，不存在同样的表面张力的问题。该方法称为“干法清洗”。
最初，使用了与去除如灰尘等污染所用的方法相同的气相法。这些技术在空气、氧或惰性气体气氛中用施加热能或紫外线能量使沾污激发。(见Engelsberg的美国专利5024968，5099557)。遗憾的是，这些系统的能量不足以去除光刻胶或很严重的沾污。
利用如公开于Nachshon的美国专利5114834和Elliott等人的WO9507152中的各种准分子激光光刻胶刻图方法可以部分地解决此问题。Nachshon指出垂直于半导体表面施加激光可以通过消融除去光刻胶。可以提供如氧或臭氧等反应气体与消融材料反应。Elliott指出最好以与半导体表面成15°的角度施加激光，以通过消融来除去光刻胶。建议使用这两种施加激光的方法，其中在第一和第二种施加方法之间将托盘旋转90°。根据Nachson的方法，可提供如氧或臭氧等反应气体，使它们与消融材料反应。
然而，这些方法仍存在不足，在100Å-200Å深度的晶片表面上残留有碳(对于1微米的光刻胶层)。Srinivasan等人(J.A ppl.Phys.61(1)，1987年1月)旨出，碳似乎并非来源于部分已燃的消融碳的再沉积，而是来源于因激光自身的瞬时高温(＞1000k)和高压(＞100atm)而产生的灰化处理的类型。在进行下一步制造步骤之前，必须将该残留物减至小于约4Å的厚度。因为紫外(UV)激光可被臭氧吸收，所以用UV光和臭氧处理去除碳残留物的努力部分仍未成功。另外，半导体制造工艺过程中还可能产生如铝或铁等金属沾污残留物。已经用激活的氯气来除去这些残留物，但这会损伤晶片。
因此，本发明的目的是研制一种不改变所述半导体衬底的表面地从半导体衬底表面上除去不希望的碳材料的方法。该方法使用低温(低于或等于200℃)并且还严格地是气相。
本发明的另一目的是提供一种为了能进行下一步半导体器件制造工艺而除去碳残留物的方法。
我们的发明是一种从衬底表面除去碳材料的方法，该方法包括在水蒸汽和分子氯气的气氛中加热所述衬底的步骤。
在优选实施例中，加热温度低于200℃，所述气氛中水蒸汽和分子氯气的比约为12∶1。
在另一优选实施例中，除碳处理与光刻胶激光消融步骤结合，提供一种从衬底材料上除去光刻胶的方法。
参考以下对优选实施例的说明和各附图，本领域的普通技术人员会了解本发明的其它目的、特点和优点，其中：
图1展示了用于除去激光刻图工艺后残留的碳残留物的装置。
本发明的处理对象是已经通过激光融蚀刻蚀了光刻胶层的Si或GaAs晶片。如上所述，该激光刻图工艺并不十分有效，在衬底表面上留下了大于约100Å厚的碳层。该层的厚度必须减薄至其它的器件制造步骤得以进行的程度。这样留下的任何碳必须在由SI MS分析检测不到的水平方可(例如，碳必须在约4Å的“本底”水平以下)。我们已研制出的方法便可达到这个要求，包括在水蒸汽和分子氯气的气氛中加热晶片。
我们的方法利用以下化学反应：
因为该气相反应能够在低于200℃的温度下以每分钟约1-2Å的速率去除碳层，所以该反应对本方法来说是极有效和极重要的。如果在较高温度下进行反应，则衬底材料会被氯腐蚀。
该反应是在已由激光融蚀对其光刻胶进行了刻图的晶片上进行的。该方法可以用来去除高达约1微米厚的残留碳，仅有时间的限制。该方法可以按两种方式进行。
按第一种方法，在激光刻图设备中进行该反应。在这种情况下，潮湿的氩混合气与分子氯混合，并被送到气体反应室。由于不能加热反应室和因水蒸汽和氯之间的所述反应而光化引起形成了气态HCl，产生了许多如对设备内部的腐蚀等问题。
按第二种方法，在一特定的改型的热炉中进行该反应，具体情况见图1。如该图所示，将石英管1置于Lindberg炉2中，其终端与水源3和氯气源4相连。将该炉相对于外部光源进行屏蔽，因为散射的UV光可能会导致形成HCl气。下面将说明普通的方法。
控制量的去离子水从水箱3通过阀5流到三通针阀6。在该点与由源7供应的惰性载体气(氮)混合，并受控地流过阀8。水在不锈钢旋管9处汽化，并由载体气体携带着通过三通阀10，以便与已通过阀11测过的来自源4的适量氯气混合。混合发生在防腐蚀的特氟隆制的管线12中。利用三通阀11从三个方面来说是有利的。首先，它可以确保蒸汽的产生；第二，它可以控制给晶片处理过程供应的蒸汽；第三，它可以在改变样品晶片时不间断地产生蒸汽。
在与水蒸汽混合之前，应加热氯气，防止其聚集。这由温度监测器13和VARIAC电流控制器14来控制。
已结合的水蒸汽/分子氯气蒸汽15进入石英管1用以处理晶片16。晶片上流下的处理后冷凝物17漏下以避免沾污。这种设备的最主要的优点在于，它远比第一种方法中所述的激光刻图单元便宜且容易修护。
水蒸汽-氯的反应应在高于100℃且低于200℃的温度下进行。在100℃以下的温度下，水蒸汽会冷凝成液相，这会损伤晶片。正如早已注意到的那样，在高于200℃的温度下，离子掺杂剂(如B或As)会扩散进衬底中。
在流速为每分钟1标准升时水蒸汽与分子氯的摩尔比最好为12∶1，这样会产生最佳效果。也可以用1∶1和15∶1之间的其它比例，但所有这些比例会导致反应速率降低，同时处理时间延长，还会增大衬底的腐蚀量。这是所不希望的。12∶1的比例最佳，因为我们发现要保持如1-2Å/min的很好反应速率需要大量的水。这样便可以去除碳。另外，比例超过12∶1时，会稀释氯，导致处理时间令人无法接受。
而且，尽管最佳流速为约每分钟1标准升，但也可用较低的流速。因为较低的流速会增加去除时间，所以这么低的流速不太好。高达20标准升/分钟的较高流速在一定程度上能加大去除速率，但要保持之很困难。
我们的最佳条件是：
温度：110-200℃，最好150℃
混合比：1∶1-15∶1，最好12∶1(摩尔)(水蒸汽∶氯)
流量：水蒸汽100-30000cc/min，最好1200cc/
min
氯50-1500cc/min，最好100cc/min
载体气(N2)50-1000cc/min，最好50cc/
min
除C速率：约1-2Å/min
使用载体气体有助于蒸汽在炉中的流动，可以是任何一种相对于水蒸汽/氯为反应惰性的气体，例如N2、Ar或空气。
应注意，这种反应的其它可能应用包括腐蚀有石墨或钻石层及由这些材料整体地构成的衬底的晶片或晶片表面的制备。在这些应用中，反应的温度不限于上述最佳范围内。该反应用于从衬底材料上去除碳，对衬底进行腐蚀。另外，该方法还可用于从衬底上去除半导体器件处理中产生的少量如Al或Fe等沾污元素。
为了简便起见，只在一个或多个附图中示出了本发明的特征。因为根据本发明每个特征可以与其它特征结合。本领域的技术人员会发现对本发明实施例的变形显然落在本发明权利要求书的范围内。
Claims (10)
1一种从衬底表面去除碳的方法，所述方法包括在含水蒸汽和分子氯气的气氛中加热衬底。
2根据权利要求1的方法，其特征在于，所述衬底的加热温度低于200℃。
3根据权利要求1的方法，其特征在于，所述衬底的加热温度高于100℃。
4根据权利要求1的方法，其特征在于，所述衬底的加热温度为150℃。
5根据权利要求1的方法，其特征在于，所述气氛中所述水蒸汽与分子氯气的摩尔比约为1∶1-15∶1。
6根据权利要求1的方法，其特征在于，在所述气氛中所述水蒸汽和分子氯气的比约为12∶1。
7根据权利要求1的方法，其特征在于，在炉中进行所述加热。
8根据权利要求1的方法，其特征在于，所述衬底选自Si和GaAs。
9一种从衬底表面去除光刻胶的方法，所述方法包括以下步骤：
a)对所述表面施加激光束，使光到胶从所述表面消融，但有碳残留；然后
b)通过在水蒸汽和分子氯气的气氛中加热所述晶片去除所述表面上的碳。
10一种从衬底表面上去除少量沾污元素的方法，所述方法包括在水蒸汽和分子氯气的气氛中加热所述衬底。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US625673 | 1996-03-29 | ||
| US08/625,673 US5998305A (en) | 1996-03-29 | 1996-03-29 | Removal of carbon from substrate surfaces |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1166051A true CN1166051A (zh) | 1997-11-26 |
| CN1113393C CN1113393C (zh) | 2003-07-02 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97110296A Expired - Fee Related CN1113393C (zh) | 1996-03-29 | 1997-03-28 | 从衬底表面除去碳的方法 |
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|---|---|
| US (2) | US5998305A (zh) |
| EP (1) | EP0798767B1 (zh) |
| JP (1) | JP3367859B2 (zh) |
| KR (1) | KR100356567B1 (zh) |
| CN (1) | CN1113393C (zh) |
| DE (1) | DE69726634T2 (zh) |
| ID (1) | ID18292A (zh) |
| IL (1) | IL120522A (zh) |
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1996
- 1996-03-29 US US08/625,673 patent/US5998305A/en not_active Expired - Lifetime
-
1997
- 1997-03-25 IL IL12052297A patent/IL120522A/xx not_active IP Right Cessation
- 1997-03-27 ID IDP971042A patent/ID18292A/id unknown
- 1997-03-28 JP JP09288797A patent/JP3367859B2/ja not_active Expired - Fee Related
- 1997-03-28 DE DE69726634T patent/DE69726634T2/de not_active Expired - Fee Related
- 1997-03-28 CN CN97110296A patent/CN1113393C/zh not_active Expired - Fee Related
- 1997-03-28 EP EP97105319A patent/EP0798767B1/en not_active Expired - Lifetime
- 1997-03-28 KR KR1019970011020A patent/KR100356567B1/ko not_active IP Right Cessation
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1999
- 1999-11-05 US US09/434,307 patent/US6242368B1/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1071713C (zh) * | 1998-11-11 | 2001-09-26 | 华南师范大学华南量子电子学研究所 | 砷化镓、磷化镓衬底干处理方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| IL120522A (en) | 2003-09-17 |
| US5998305A (en) | 1999-12-07 |
| DE69726634D1 (de) | 2004-01-22 |
| DE69726634T2 (de) | 2004-09-30 |
| EP0798767A3 (en) | 1998-03-11 |
| ID18292A (id) | 1998-03-26 |
| JPH1032193A (ja) | 1998-02-03 |
| US6242368B1 (en) | 2001-06-05 |
| KR970067682A (ko) | 1997-10-13 |
| CN1113393C (zh) | 2003-07-02 |
| JP3367859B2 (ja) | 2003-01-20 |
| KR100356567B1 (ko) | 2002-12-18 |
| EP0798767A2 (en) | 1997-10-01 |
| IL120522A0 (en) | 1997-07-13 |
| EP0798767B1 (en) | 2003-12-10 |
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