CN1052513A - 各向异性腐蚀硅片的改进方法与硅片腐蚀溶液 - Google Patents
各向异性腐蚀硅片的改进方法与硅片腐蚀溶液 Download PDFInfo
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- 239000010703 silicon Substances 0.000 title claims abstract description 41
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- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
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Abstract
一种各向异性腐蚀(100)硅片晶面的改进方法,
它包括将其硅晶片浸渍在腐蚀溶液中,其腐蚀溶液含
有一种芳族化合物,该芳族化合物苯环上具有至少两
个相临的羟基和一个极性官能团,一种胺和水。达到
了高质量的腐蚀,其速率高得多。
Description
本发明涉及硅的腐蚀,更具体地说,本发明涉及改进单晶硅各向异性的腐蚀。
在微电子设备的生产中,多年来都采用单晶硅的各向异性腐蚀。一个主要的特点是,腐蚀溶液腐蚀(100)晶面的速率比腐蚀(110)和(111)晶面要快得多,(110)和(111)晶面与(100)晶面形成54.74°而构成V形的侧壁。现有技术中已知的腐蚀溶液举例如下:IBM Tech.Discl.Bull.,vol.19,No.9(2.1977),P3623公开了一种用于各向异性腐蚀单晶硅的溶液,其溶液含1,2-乙二胺、焦儿茶酚和水;和IBM Tech.Discl.Bull.,Vol.19,No.10(3,1977),P3953也描述了这样一种溶液,其溶液含有前述文章中所述的三种组分,而且还含有过氧化氢。
另外还可参见1983年11月29日公开的Bohlen等人的US4417946和1982年8月3日公开的Bohlen等人的US4342817,这两篇专利公开了一种制造膜片的方法,使用的腐蚀溶液由1,2-乙二胺、焦儿茶酚、水和任选的过氧化氢所组成,以及1981年10月6日公开的Greenwood的US4293373和1980年10月28日公开的Greenwood的US4229979,这两篇专利公开了一种制造硅转换器的方法,该方法包含用含有1,2-乙二胺、焦儿茶酚和水的溶液腐蚀掺杂硼的硅片。
还注意到,1972年3月21日公开的Shipley,Jr.等人的US3650957,该专利公开了一种用于腐蚀铜的溶液,这种溶液包含铜离子源、铜离子的络合剂,如羟基羧酸或链烷醇胺、氯离子或溴离子源和可溶解钼、钨或钒化合物的溶液。
1975年3月25日公开的Sterenson的US3873203公开了含有酰肼和焦儿茶酚的腐蚀硅的混合物。
此外,1964年12月8日公开的Hall等人的US3160539涉及硅的腐蚀溶液,其中含哌啶。
IBM Tech.Discl.Bull.,Vol.15,No.1(6.1972)P.173公开了铝的腐蚀剂,它是由诸如哌啶或吡咯烷之类的仲有机胺水溶液组成。
另外,Beechko于1986年6月18日提出的美国专利申请号NO.875833中公开了一种腐蚀单晶硅的特别有效的溶液。这种溶液包含乙醇胺、焦儿茶酚、水、过氧化氢和哌啶。已发现,该溶液腐蚀(100)硅晶面的速率约为40μ/小时。
目前,已研制出一种腐蚀硅的改进方法,其中包括让硅与一种腐蚀溶液接触,其腐蚀溶液包含在苯环上至少有两个相临的羟基和一个极性官团的芳族化合物、一种胺和水。本发明的目的本质上也是腐蚀溶液。
根据本发明,(100)硅晶面的腐蚀速率已达到约125-140μ/小时。例如,这种速率比上述Beechko申请中采用的腐蚀溶液一般所达到速率高三倍。并且,这种腐蚀溶液的工业应用是相当安全的,在环境方面也是与现行的处理技术相适应的。
实施本发明时,最好将待腐蚀的硅片浸渍在腐蚀液中。这里使用的温度较好的是100-125℃,更好的是约115-125℃。其实际的温度和时间可以改变,然而要取决于诸多因素,如所要求的腐蚀速率,待腐蚀的几何形状,所使用的确切组成等。而这些对于本技术领域的技术人员来说都是显而易见的。此外,在大多数情况下溶液的pH范围为约11-12更可取。
正如上面所述,本发明使用的腐蚀溶液含有苯环上至少有两个相临的羟基和一个极性官能团的芳族化合物。具有代表性的极性官能团是COOH、SO2OH或NO2,更可取的是COOH。适宜的芳族化合物如下述的化合物:
1,2-二羟基苯-3,5-二磺酸;
6,7-二羟基-2-萘磺酸;
3,4-二羟基苯甲酸;
2,3-二羟基苯甲酸;
4-硝基儿茶酚;和
七叶亭(6,7-二羟香豆素)。
在特别优选的实施例中,芳族化合物是梧酸。本发明的腐蚀溶液可以使用极性相当高的任何适宜的胺化合物。例如,适宜的胺如下:
a、伯脂肪胺包括一元胺、二胺和三胺。这些胺一般含2-8个碳原子,更可取为2-6个碳原子,例如:乙胺、正丙胺、正丁胺、正戊胺、正己胺、1,2-乙二胺、二氨基丙烷、二氨基丁胺、戊二胺、间-亚二甲苯基二胺和二亚乙基三胺。该组中特别可取的胺是碳原子数2-4的二胺,例如1,2-乙二胺和二氨基丙烷。
b、链烷醇胺,即脂族羟基胺。这些胺中每个链烷醇基通常含2-5个碳原子。具体的例子有:单乙醇胺、二乙醇胺、三乙醇胺、单-、二-、三-丙醇胺、乙醇丙醇胺、二乙醇丙醇胺、单-、二-、三-丙醇胺。特别可取的链烷醇胺是每个链烷醇基有2-3个碳原子,例如乙醇胺类、丙醇胺类和乙醇丙醇胺类。
本发明特别可取的实施方式中使用单-乙醇胺。
尽管组分的比例变化范围可以很宽,但腐蚀溶液可取地是含约3-6(摩尔)%芳族化合物,约32-65(摩尔)%胺和约65-38(摩尔)%水。更可取地是,腐蚀溶液含约4-6(摩尔)%芳族化合物、约39-56(摩尔)%胺和约57-38(摩尔)%水。
腐蚀溶液还可加其他各种组分。例如,可以加入少量的(如0.2-0.3(摩尔)%吡嗪或哌啶或过氧化氢(例如0.5-3ml/1000ml胺化合物)以进一步提高该溶液的腐蚀速率。此外,可以加入少量的表面活性剂(例如0.5-3ml/1000ml胺化合物),如由Minnesota Mining & Manufacturing Company生产的“FC-129”,或其他氟化烃表面活性剂。希望有表面活性剂,这是因为表面活性剂显然是通过阻止释放出的氢气泡附着在腐蚀表面而提高腐蚀的均匀性。
本发明的腐蚀溶液提供高质量的腐蚀,凹孔、异常析出与刻面小,腐蚀速率非常高。就此而论,在许多的应用中都希望使用本发明。例如,还可使用该腐蚀溶液以US4342817中描述的方式腐蚀掺杂磷的硅片,该专利整个公开的内容在这里可供参考。
在一个可取的应用中,可使用该腐蚀溶液高速率(约125-140μ/小时)腐蚀(100)硅晶面,而在掺杂硼高的界面处停止腐蚀,在厚的硅片表面上形成大而薄的富硼窗口。这些硅产品用于生产X-射线和电子束遮拦片。
除了腐蚀单晶硅,本发明的腐蚀溶液也能有效腐蚀其他硅,如多晶硅或外延生长硅。
下述实施例说明本发明。
实例1
在一个派热克斯耐热硬质玻璃反应器(250mm×200mm)中装入3升单-乙醇胺和600毫升去离子水。由粉剂漏斗加入900克梧酸,再用300ml去离子水冲洗漏斗。再加入20克吡嗪、4.5毫升表面活性剂(“FC-129”)和7.5毫升30%过氧化氢,其琥珀色溶液在水冷凝器中回流。
将该晶片浸入腐蚀溶液中于温度约118-120℃下腐蚀(100)硅晶面取向的硅片达约4-4.5小时。该腐蚀溶液腐蚀(100)硅的速率约为94μ/小时。参见下列表Ⅰ。
实例2
在一个派热克斯耐热硬质玻璃反应器(250mm×200mm)中装入1400毫升去离子水,1150克梧酸、20克吡嗪、3800毫升单-乙醇胺和7毫升表面活性剂(“FC-129”)。该溶液在水冷凝器中加热回流。
将该晶片浸入腐蚀溶液中于温度约119℃下腐蚀(100)硅晶面取向的硅片达约5.5小时。该腐蚀溶液腐蚀(100)硅的速率约为125μ/小时。参见下列表Ⅰ。
实例3
在500毫升派热克斯耐热硬质玻璃反应锅中装入335毫升单-乙醇胺和75毫升去离子水。由粉剂漏斗加入100.4克梧酸。再加25毫升哌啶、1毫升表面活性剂(“FC-129”)和3毫升30%过氧化氢。该琥珀色溶液在水冷凝器中回流。
将该晶片浸入腐蚀溶液中于温度约125℃下腐蚀(100)硅晶面取向的硅片达约10小时。该腐蚀溶液腐蚀(100)硅的速率约为60-70μ/小时。参见下列表Ⅰ。
对比实施例A-G
为了对比,用表Ⅰ列出的组成重复实施例3的方法。在每个对比实施例中,不是像前面叙述时所限定的那样,其组成中用芳族化合物代替梧酸。对于每一种情况,发现其(100)硅的腐蚀速率结果都是不可接受的。在下列表Ⅰ中汇集了这些组成及其相应的结果。
表Ⅰ
实例 对比例
组成 1 2 3 A B C D E F G
单乙醇胺 × × × × × × × × × ×
哌啶 × × × × × × × ×
吡嗪 × ×
水 × × × × × × × × × ×
表示活性剂 × × × × × × × ×
(FC-129) × × × × × × × ×
过氧化氢 × × × × × × ×
梧酸 × × ×
酯氢酯 ×
1,2-萘醌 ×
-4-磺酸 ×
茜素 ×
醌茜素 ×
2,3-二羟基吡啶 ×
3,6-二羟基哒嗪 ×
1,2-萘醌 ×
儿茶酚 ×
腐蚀结果*
腐蚀速率,94 125 60-70 S N N N N NS VS
μ/小时
*使用下列缩写,S:慢;N:无;VS:很慢;NS:非选择的
实施例4-8
除了溶液中水量不同外,使用组分相同、其相对比例也相同的溶液实施实施例1的方法。其结果汇集于下表Ⅱ。
表Ⅱ
水量,摩尔% 腐蚀速率,μ/小时
实施例
4 41 113
5 46 133
6 51 140
7 53 140
8 57 137
Claims (28)
1、一种腐蚀硅的方法,其特征在于,所述的硅与腐蚀溶液接触,其腐蚀溶液含有在苯环上至少有两个相临的羟基和一个极性官能团的芳族化合物、一种胺和水。
2、根据权利要求1所述的方法,其特征在于所述的极性官能团是COOH。
3、根据权利要求2所述的方法,其特征在于所述的芳族化合物是梧酸。
4、根据权利要求1所述的方法,其特征在于,所述的胺选自于由具有2-4碳原子的二胺与链烷醇胺组成的组中,链烷醇胺中每个链烷醇基含2-3碳原子。
5、根据权利要求4所述的方法,其特征在于所述的胺是单乙醇胺。
6、根据权利要求1所述的方法,其特征在于所述的腐蚀溶液还包含吡嗪或哌啶。
7、根据权利要求1所述的方法,其特征在于将过氧化氢加到所述的腐蚀溶液中。
8、根据权利要求1所述的方法,其特征在于将表面活性剂加到所述的腐蚀溶液中。
9、根据权利要求1所述的方法,其特征在于,所述的腐蚀溶液包含约4-6(摩尔)%所述芳族化合物、约39-56(摩尔)%所述胺和约57-38(摩尔)%水。
10、根据权利要求1所述的方法,其特征在于所述腐蚀溶液的温度约115-125℃,pH约11-12。
11、一种腐蚀硅片的方法,其特征在于将所述的硅片放入一种腐蚀溶液中,其溶液包含约4-6(摩尔)%芳族化合物,该芳族化合物的苯环上至少有两个相临的羟基和一个COOH基;约39-56(摩尔)%胺,其胺选自于由具有2-4碳原子的二胺与链烷醇胺组成的组中,而链烷醇胺的每个链烷醇基含2-3个碳原子;以及约57-38(摩尔)%水。
12、根据权利要求11所述的方法,其特征在于所述的芳族化合物是梧酸,所述的胺是单乙醇胺。
13、根据权利要求12所述的方法,其特征在于所述腐蚀溶液的温度约115-125℃,pH约11-12。
14、根据权利要求13所述的方法,其特征在于所述的腐蚀溶液还含有吡嗪或吡啶。
15、根据权利要求14所述的方法,其特征在于将过氧化氢加到所述的腐蚀溶液中。
16、根据权利要求15所述的方法,其特征在于将一种表面活性剂加入到所述的腐蚀溶液中。
17、一种硅的腐蚀溶液,其特征在于,它含有在苯环上具有至少两个相临的羟基和一个极性官能团的芳族化合物,一种胺和水。
18、根据权利要求17所述的腐蚀溶液,其特征在于所述的极性官能团是COOH。
19、根据权利要求18所述的腐蚀溶液,其特征在于所述的芳族化合物是梧酸。
20、根据权利要求17所述的腐蚀溶液,其特征在于,所述的胺选自于由具有2-4个碳原子的二胺与链烷醇胺组成的组中,其链烷醇胺中的每个链烷醇基含2-3个碳原子。
21、根据权利要求20所述的腐蚀溶液,其特征在于所述的胺是单乙醇胺。
22、根据权利要求17所述的腐蚀溶液,其特征在于它还包含吡嗪或哌啶。
23、根据权利要求17所述的腐蚀溶液,其特征在于它还包含一种表面活性剂。
24、根据权利要求17所述的腐蚀溶液,其特征在于它包含有约4-6(摩尔)%所述芳族化合物,约39-56(摩尔)%所述胺和约57-38(摩尔)%水。
25、一种硅的腐蚀溶液,其特征在于它含有约4-6(摩尔)%芳族化合物,其芳族化合物的苯环上具有至少两个相临的羟基和一个COOH基;约39-56(摩尔)%胺,它选自于由具有2-4碳原子的二胺与链烷醇胺组成的组中,其链烷醇胺的每个链烷醇基含2-3碳原子;以及约57-38(摩尔)%水。
26、根据权利要求25所述的腐蚀溶液,其特征在于所述的芳族化合物是梧酸,所述胺是单乙醇胺。
27、根据权利要求26所述的腐蚀溶液,其特征在于它还含吡嗪或哌啶。
28、根据权利要求27所述的腐蚀溶液,其特征在于它还含有一种表面活性剂。
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Application Number | Priority Date | Filing Date | Title |
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US07/416,337 US4941941A (en) | 1989-10-03 | 1989-10-03 | Method of anisotropically etching silicon wafers and wafer etching solution |
US416,337 | 1989-10-03 |
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CN1052513A true CN1052513A (zh) | 1991-06-26 |
CN1024148C CN1024148C (zh) | 1994-04-06 |
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CN90108439A Expired - Lifetime CN1024148C (zh) | 1989-10-03 | 1990-09-26 | 各向异性腐蚀硅片的改进方法与硅片腐蚀溶液 |
Country Status (8)
Country | Link |
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US (1) | US4941941A (zh) |
EP (1) | EP0421093B1 (zh) |
JP (1) | JPH0713956B2 (zh) |
KR (1) | KR940008369B1 (zh) |
CN (1) | CN1024148C (zh) |
AU (1) | AU636388B2 (zh) |
DE (1) | DE69022944T2 (zh) |
MY (1) | MY105972A (zh) |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN111410963A (zh) * | 2019-01-08 | 2020-07-14 | 三星电子株式会社 | 硅层刻蚀剂组合物、制备其的方法及形成图案的方法 |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040018949A1 (en) * | 1990-11-05 | 2004-01-29 | Wai Mun Lee | Semiconductor process residue removal composition and process |
US6187730B1 (en) | 1990-11-05 | 2001-02-13 | Ekc Technology, Inc. | Hydroxylamine-gallic compound composition and process |
US6242400B1 (en) | 1990-11-05 | 2001-06-05 | Ekc Technology, Inc. | Method of stripping resists from substrates using hydroxylamine and alkanolamine |
US6110881A (en) * | 1990-11-05 | 2000-08-29 | Ekc Technology, Inc. | Cleaning solutions including nucleophilic amine compound having reduction and oxidation potentials |
US6000411A (en) * | 1990-11-05 | 1999-12-14 | Ekc Technology, Inc. | Cleaning compositions for removing etching residue and method of using |
US6492311B2 (en) | 1990-11-05 | 2002-12-10 | Ekc Technology, Inc. | Ethyenediaminetetraacetic acid or its ammonium salt semiconductor process residue removal composition and process |
US7205265B2 (en) * | 1990-11-05 | 2007-04-17 | Ekc Technology, Inc. | Cleaning compositions and methods of use thereof |
US6121217A (en) | 1990-11-05 | 2000-09-19 | Ekc Technology, Inc. | Alkanolamine semiconductor process residue removal composition and process |
US5279771A (en) * | 1990-11-05 | 1994-01-18 | Ekc Technology, Inc. | Stripping compositions comprising hydroxylamine and alkanolamine |
JPH0763061B2 (ja) * | 1991-07-30 | 1995-07-05 | インターナショナル・ビジネス・マシーンズ・コーポレイション | 選ばれた触媒が加えられたエッチング剤を用いるシリコンの異方性エッチングの制御 |
US5431777A (en) * | 1992-09-17 | 1995-07-11 | International Business Machines Corporation | Methods and compositions for the selective etching of silicon |
US7144849B2 (en) * | 1993-06-21 | 2006-12-05 | Ekc Technology, Inc. | Cleaning solutions including nucleophilic amine compound having reduction and oxidation potentials |
US5419779A (en) * | 1993-12-02 | 1995-05-30 | Ashland Inc. | Stripping with aqueous composition containing hydroxylamine and an alkanolamine |
US5597420A (en) * | 1995-01-17 | 1997-01-28 | Ashland Inc. | Stripping composition having monoethanolamine |
US5804090A (en) * | 1995-03-20 | 1998-09-08 | Nissan Motor Co., Ltd. | Process for etching semiconductors using a hydrazine and metal hydroxide-containing etching solution |
DE19624315C2 (de) * | 1996-06-18 | 1998-06-10 | Fraunhofer Ges Forschung | Verfahren zum Ätzen von Strukturen in einer Siliziumschicht |
DE19624316C2 (de) * | 1996-06-18 | 1998-04-30 | Fraunhofer Ges Forschung | Verfahren zum Bilden von Justiermarken in einer Siliziumschicht |
US6423646B1 (en) * | 1998-06-04 | 2002-07-23 | Vanguard International Semiconductor Corporation | Method for removing etch-induced polymer film and damaged silicon layer from a silicon surface |
US6586955B2 (en) | 2000-03-13 | 2003-07-01 | Tessera, Inc. | Methods and structures for electronic probing arrays |
KR20020023286A (ko) * | 2002-01-10 | 2002-03-28 | 조태봉 | 프리핸디퍼티 |
DE102007026081A1 (de) * | 2007-05-25 | 2008-11-27 | Gebr. Schmid Gmbh & Co. | Verfahren zur Behandlung von Siliziumwafern, Behandlungsflüssigkeit und Siliziumwafer |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3160539A (en) * | 1958-09-08 | 1964-12-08 | Trw Semiconductors Inc | Surface treatment of silicon |
NL246263A (zh) * | 1959-07-27 | 1900-01-01 | ||
US3650957A (en) * | 1970-07-24 | 1972-03-21 | Shipley Co | Etchant for cupreous metals |
US3873203A (en) * | 1973-03-19 | 1975-03-25 | Motorola Inc | Durable high resolution silicon template |
US4155866A (en) * | 1978-04-24 | 1979-05-22 | International Business Machines Corporation | Method of controlling silicon wafer etching rates-utilizing a diazine catalyzed etchant |
GB1588669A (en) * | 1978-05-30 | 1981-04-29 | Standard Telephones Cables Ltd | Silicon transducer |
DE2922416A1 (de) * | 1979-06-01 | 1980-12-11 | Ibm Deutschland | Schattenwurfmaske zum strukturieren von oberflaechenbereichen und verfahren zu ihrer herstellung |
JPS5855323A (ja) * | 1981-09-26 | 1983-04-01 | Toshiba Corp | シリコン及びシリコン酸化膜の腐食液 |
US4929301A (en) * | 1986-06-18 | 1990-05-29 | International Business Machines Corporation | Anisotropic etching method and etchant |
-
1989
- 1989-10-03 US US07/416,337 patent/US4941941A/en not_active Expired - Lifetime
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1990
- 1990-08-11 EP EP90115482A patent/EP0421093B1/en not_active Expired - Lifetime
- 1990-08-11 DE DE69022944T patent/DE69022944T2/de not_active Expired - Fee Related
- 1990-08-30 JP JP2226819A patent/JPH0713956B2/ja not_active Expired - Fee Related
- 1990-09-14 MY MYPI90001597A patent/MY105972A/en unknown
- 1990-09-24 AU AU63141/90A patent/AU636388B2/en not_active Ceased
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CN111410963A (zh) * | 2019-01-08 | 2020-07-14 | 三星电子株式会社 | 硅层刻蚀剂组合物、制备其的方法及形成图案的方法 |
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Publication number | Publication date |
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EP0421093A1 (en) | 1991-04-10 |
JPH0713956B2 (ja) | 1995-02-15 |
JPH03126227A (ja) | 1991-05-29 |
AU6314190A (en) | 1991-04-11 |
CN1024148C (zh) | 1994-04-06 |
KR910008852A (ko) | 1991-05-31 |
DE69022944D1 (de) | 1995-11-16 |
EP0421093B1 (en) | 1995-10-11 |
KR940008369B1 (ko) | 1994-09-12 |
US4941941A (en) | 1990-07-17 |
MY105972A (en) | 1995-02-28 |
DE69022944T2 (de) | 1996-05-30 |
AU636388B2 (en) | 1993-04-29 |
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