CN1813223B - 适合用来除去光刻胶、光刻胶副产物和蚀刻残余物的组合物及其应用 - Google Patents
适合用来除去光刻胶、光刻胶副产物和蚀刻残余物的组合物及其应用 Download PDFInfo
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- CN1813223B CN1813223B CN2004800184391A CN200480018439A CN1813223B CN 1813223 B CN1813223 B CN 1813223B CN 2004800184391 A CN2004800184391 A CN 2004800184391A CN 200480018439 A CN200480018439 A CN 200480018439A CN 1813223 B CN1813223 B CN 1813223B
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Abstract
包含某些胺和/或季铵化合物、羟胺、缓蚀剂、有机稀释剂和任选的水的组合物,能够从基片上除去光刻胶、光刻胶副产物和残余物,以及蚀刻残余物。
Description
技术领域
本发明涉及从基片上选择性地除去光刻胶、光刻胶副产物和残余物以及蚀刻残余物,该组合物特别用来选择性地除去这些物质,但是却不会腐蚀暴露于该组合物之下的金属。另外,本发明涉及一些适合用来除去这些材料的组合物。
背景技术
微电子组件的制造中,例如包括在制造集成电路的芯片和芯片的封装时(用来连接和保护芯片的制品)中的许多步骤是蚀刻过程。因此,近年来已经开发了许多种不同种类的蚀刻法来除去材料,有时是在选择性的区域除去材料,这些蚀刻法得到了不同程度的应用。另外,对例如构成最终集成电路芯片的不同层进行蚀刻的步骤是最关键、最决定性的步骤。
正性胶已经被广泛地用作掩模材料,用来在基片上形成图案,和形成通路,从而能够随后蚀刻图案、或在基片中形成图案。制造基片的最后步骤包括从基片上除去未曝光的光刻胶材料。然而,另外使用等离子体蚀刻、反应离子蚀刻或离子铣在基片中形成图案和形成通路,这使得光刻胶掩模材料极难除去。
例如,在高级DRAMS和具有线路互联后端多层布线的逻辑装置之类的复合半导体设备中,用反应离子蚀刻(RIE)产生贯通层间电介质的通路,从而使一个水平面上的硅、硅化物或金属布线与下一个水平面上的布线提供接触。这些通路通常露出Al、AlCu、Cu、Ti、TiN、Ta、TaN、硅或硅化物,例如钨、钛或钴的硅化物。RIE法留下了复杂混合物的残余物,该残余物可包括再溅射(resputtered)的氧化物材料,还可能含有来自用于形成通路的光刻胶中的少量有机材料。
同样,在制造例如铝、铜及其合金的导电线路时,导电线路上会有蚀刻残余物,这些残余物必须除去。
因此需要提供一种能够除去光刻胶和蚀刻(特别是等离子体蚀刻、RIE或离子铣蚀刻)产生的残余物的选择性方法。另外,需要提供一种能够除去光刻胶蚀刻残余物的选择性方法,相对于这种方法对也可能暴露于清洗组合物之下的金属、硅、硅化物和/或淀积的氧化物之类的内层介质的去除作用而言,该方法对残余物具有高选择性。
发明内容
本发明提供一种能够从基片上选择性地除去光刻胶、光刻胶副产物、光刻胶残余物和/或蚀刻残余物,而不会腐蚀也可能暴露于该组合物的金属的组合物。另外,本发明提供具有最小金属浸蚀速率的组合物。
更具体地讲,本发明涉及包含以下组成的组合物:
a)约25-75重量%的至少一种下式表示的胺:NR1R2R3,式中R1、R2和R3各自独立地选自H、脂族基、醚基、烷基单胺、烷基二胺、烷基三胺、环中任选包含至少一个选自N、O和S的其它杂原子的N杂环基;或至少一种化学式[NR4,R5,R6,R7]-OH表示的季铵化合物,式中R4、R5、R6和R7各自独立地为烷基;
b)约10-25重量%羟胺;
c)约0-32重量%有机稀释剂;
d)约10-30重量%水;
并且该组合物的pH大于7。
本发明的另一个方面涉及一种用来从基片上除去后蚀刻残余物、残余的光刻胶和/或光刻胶副产物的方法,该方法包括使基片与上述组合物接触。
本发明的又一个方面涉及从基片上除去光刻胶的方法,该方法包括使基片与上述组合物接触。
通过以下详述,本发明的其它目的和优点对本领域技术人员将是显而易见的,在以下详述中,通过简单地举例说明本发明预期的最佳实施方式,仅显示并描述了本发明的优选实施方式。人们将认识到,在不背离本发明的基础上,本发明可以有其它的不同实施方式,也可在许多显而易见的方面对本发明的一些细节进行修改。因此,附图和描述视为对本发明的说明而非限制。
附图说明
图1是清洗之前具有侧壁聚合物的金属线路的SEM照片。
图2是用根据本发明的组合物对图1的金属线路进行清洗之后的SEM照片。
图3是清洗之前具有蚀刻残余物的后蚀刻通路的SEM照片。
图是用根据本发明的组合物对图3的后蚀刻通路进行清理之后的SEM照片。
本发明的各种最佳实施方式
本发明涉及选择性地除去光刻胶和/或蚀刻残余物,特别是但不限于由反应离子蚀刻产生的残余物。另外,所述光刻胶和/或蚀刻残余物存在于也包括金属、硅、硅酸盐和/或沉积二氧化硅之类内层(interlevel)介电材料的制品之上或之内,所述光刻胶和/或残余物与金属、硅、硅化物和/或内层介电材料都将与清洗组合物相接触。所述金属通常为铜、铜合金、钛、氮化钛、钽、氮化钽、铝和/或铝合金。根据本发明除去的残余物优选为,但不限于受到反应离子蚀刻处理的残余物。
本发明的组合物通常包含约25-75重量%,更通常约25-40重量%,优选约25-30重量%的至少一种化学式NR1R2R3表示的胺,式中R1、R2和R3各自独立地选自H、脂族基、醚基、烷基单氨基、烷基二氨基、烷基三氨基、环中任选地包含至少一个选自N、O和S的另外的杂原子的N杂环基;或至少一种化学式[NR4R5R6R7]-OH表示的季铵化合物,式中R4、R5、R6和R7各自独立地是烷基。
合适的脂族基包括直链或支链的烷基、亚烷基、炔基、芳基、芳基-烷基、烷基-芳基和取代芳基。
醚基包括通常包含1-12个碳原子的丙烯酸醚。
氨基包括伯胺、仲胺和叔胺,以及高级烷基氨基官能团,例如二胺和三胺。
下面列出了用来描述本发明的各种术语的定义。除非有特殊情况下(单独的基团或更大基团的一部分)的限制,这些术语的定义将用于本说明书全文。
术语“烷基”表示1-20个碳原子,优选1-8个碳原子的直链或支链未取的代烃基。短语“低级烷基”表示1-4个碳原子的烷基。
术语“烯基”和“炔基”表示通常包含2-8个碳原子的直链或支链不饱和烃基。
术语“芳基”表示在环部分中包含6-12个碳原子的单环或双环芳烃基团,例如苯基、萘基、联苯基和二苯基,这些基团可被取代。
一些单环杂环基团的例子通常在环中包含5或6个原子,包括吗啉基(morpholino)、哌嗪、异噻唑、咪唑啉、吡唑啉、吡唑烷、嘧啶、吡嗪。
一些醚基的例子为甲氧基、乙氧基、丙氧基、丁氧基、异丙氧基、异丁氧基、仲丁氧基和叔丁氧基。
合适的烷基的例子包括甲基、乙基和丙基。
优选的芳基为苯基。
术语“芳烷基”或“烷基芳基”表示与烷基直接相连的芳基,例如苄基或苯乙基。术语“取代芳基”或“取代烷基芳基”表示例如被1-4个以下取代基取代的芳基或烷基芳基:例如烷基;取代烷基、卤素、三氟甲氧基、三氟甲基、羟基、烷氧基、叠氮基、环烷氧基、杂环氧基、烷酰基、烷酰氧基、氨基、烷基氨基、芳烷基氨基、羟烷基、氨基烷基、叠氮基烷基、烯基、炔基、丙二烯基(allenyl)、环烷基氨基、杂环氨基、二烷基氨基、硫醇、烷基硫代、环烷基硫代、杂环硫代、脲基、硝基、氰基、羧基、羧基烷基、氨基甲酰、烷氧羰基、烷基硫羰、芳基硫羰、烷基磺酰、磺酰胺、芳氧基等。这些取代基还可被卤素、羟基、烷基、烷氧基、芳基、取代芳基、取代烷基或芳烷基取代。“取代苄基”表示例如被上述用来取代苯基的任意基团取代的苄基。
根据本发明,优选使用的胺是氨基丙基吗啉之类的氨基烷基吗啉类和氨基乙基哌嗪之类的氨基烷基哌嗪类。
本发明的组合物通常还包含约5-25重量%,更通常约10-20重量%,优选约12-18重量%的羟胺。羟胺的化学式为NH2OH。
本发明的组合物通常还包含约0-32重量%,更通常约10-30重量%,优选约15-30重量%,最优选约20-30重量%的有机稀释剂。该有机稀释剂可与水互溶。通常根据本发明所用的有机稀释剂是醇,更具体来说是至少一种下式表示的醇:
R11-(CHOH)n-R12;
R11-(CHOH)n-R12-(CH2OH)m-R13和
R11-(CHOH)n(CR12OH)mR13,式中n是1-20的整数,优选为1-4的整数,m为1-20的整数,优选为1-4的整数,R11、R12和R13各自独立地为H、烷基、芳基或烷氧基。
合适的烷基例子为包含1-20个碳原子、优选1-8个碳原子、最优选1-4个碳原子的直链或支链未取代烃基。
合适的芳基包括环部分中包含6-12个碳原子的单环或双环烃基,例如苯基、萘基;联苯基和二苯基。优选的芳基为苯基。
合适烷基的例子包括甲基、乙基和丙基。
通常烷氧基包含1-12个碳原子。一些烷氧基的例子为甲氧基、乙氧基、丙氧基、丁氧基、异丙氧基、异丁氧基、仲丁氧基和叔丁氧基。
一些常规的有机稀释剂的例子为丙二醇、二缩三丙二醇甲基醚、1,4-丁二醇、丙二醇丙醚、二甘醇正丁醚(例如可在市场上购得的商品名为Dowanol DB的二甘醇正丁醚),己氧基丙基胺、聚(氧乙烯)二胺和四氢糠醇(THFA)。优选的稀释剂为醇。
需要时可使用稀释剂的混合物。
根据本发明的组合物还可任选地包含缓蚀剂。优选当该组合物用于金属基材时使用缓蚀剂。
缓蚀剂的例子为芳香族羟基化合物、炔醇、含羧基的化合物及其酸酐和三唑化合物。
示例性的芳香族羟基化合物包括苯酚、甲酚、二甲苯酚、邻苯二酚、间苯二酚、对苯二酚、连苯三酚、1.2.4-苯三酚(benzenetriol)、水杨醇、对羟基苄醇、邻羟基苄醇、对羟基苯乙醇、对氨基苯酚、间氨基苯酚、二氨基苯酚、氨基间苯二酚、对羟基苯甲酸、邻羟基苯甲酸、2,4-二羟基苯甲酸、2-5-二羟基苯甲酸、3,4-二羟基苯甲酸和3,5-二羟基苯甲酸。
示例性的炔醇包括2-丁炔-1,4-二醇、3,5-二甲基-1-己炔-3-醇、2-甲基-3-丁炔-2-醇、3-甲基-1-戊炔-3-醇、3,6-二甲基-4-辛炔-3,6-二醇,2,4-7,9-四甲基-5-癸炔-4,7-二醇和2,5-二甲基-3-己炔2,5-二醇。
示例性的含羧基的有机化合物及其酸酐包括甲酸、乙酸、丙酸、丁酸、异丁酸、乙二酸、丙二酸、丁二酸、戊二酸、马来酸、富马酸、苯甲酸、邻苯二甲酸、1,2,3-苯三甲酸、羟基乙酸、乳酸、苹果酸和柠檬酸、乙酸酐和水杨酸。
示例性的三唑化合物包括苯并三唑、邻甲苯三唑、间甲苯三唑、对甲苯三唑、羧基苯并三唑、1-羟基苯并三唑、硝基苯并三唑和二羟基丙基苯并三唑。
优选的缓蚀剂为邻苯二酚、五倍子酸、连苯三酚、4-甲基邻苯二酚富马酸和二乙基羟胺(DEHA)。
当使用缓蚀剂时,缓蚀剂的含量通常约为1-25重量%,更通常约1-7重量%,优选约为3-5重量%.
该组合物也包含水。水的量通常约10-30重量%。
本发明组合物的pH通常大于7,更通常约为7.5-13。
本发明的组合物不含或至少基本不含链烷醇胺(即最多可包含小于10%的链烷醇胺)。
本发明的组合物能够有效地除去很多种正性光刻胶,例如含酯或邻萘醌的光刻胶和线型酚醛清漆类的粘合剂,以及含嵌段的聚羟基苯乙烯或聚羟基苯乙烯与光致生酸剂共聚物的化学放大的光刻胶。具有本发明去胶组合物的去胶组合物能够有效将其从基片上除去的、而且可在市场上购得的光刻胶组合物的例子包括Clariant有限公司的AZ1518,AZ4620,Shipley有限公司的光刻胶S1400,APEX-ETM正性DUV,UV5TM正性DUV,MegapositTM SPRTM220系列;JSR微电子光刻胶KRF系列,ARF系列;和Tokyo Ohka Kogyo有限公司的光刻胶TSCR系列和TDUR-P/N系列。
本发明组合物能够从其上除去光刻胶和/或蚀刻后残余物,而不会腐蚀基片本身的基片包括铝钛/钨和铝/硅、铝/硅/铜之类的金属基片;以及二氧化硅、氮化硅和砷化镓之类的基片。
根据本发明的除去光刻胶和/或后蚀刻残余物的方法可包括将光刻胶施涂在基片上形成光刻胶层;通过掩模图案使施涂的光刻胶层曝光,并通过常用的方法使曝光的光刻胶层显影形成光刻胶图案;通过已知的方法使基片贯穿(thorugh)光刻胶图案;任选地任选地进行其它改性处理,例如灰化和离子注入;通过浸入之类的合适方法使基片与本发明的光刻胶组合物接触。
以下实施例用来进一步说明本发明,但是并非对本发明构成限制。
实施例1
实施例2
实施例3
实施例4
实施例5
实施例6
实施例7
实施例8
实施例9
实施例10
测试上述制剂的腐蚀速率。根据ASTM步骤F533-02a用于测试硅芯片厚度和厚度变化的标准测试法测量当基片暴露于本发明的制剂时,缓蚀剂的抗腐蚀能力。一些铝和钛的腐蚀速率结果如下:
测试在75℃下进行。结果的单位为A/分钟。
进行了清洗试验,在此试验中使具有蚀刻后残余物的结构与本发明的组合物接触,然后用去离子水洗,再用N2干燥。对比图1和图2,图1显示用本发明的组合物清洗之前的具有侧壁聚合物的金属线路的扫描电子显微照片,图2显示在65℃用实施例2的组合物清洗15分钟的金属线路的扫描电子显微照片。
对比图3和图4,图3显示用本发明的组合物清洗之前的具有蚀刻残余物的后蚀刻通路的扫描电子显微照片,图4显示在75℃用实施例2的组合物清洗15分钟的后蚀刻通路的扫描电子显微照片。
本发明以上的描述举例说明并描述了本发明。另外,说明书仅显示和描述了本发明的优选实施方式,但是如上所述,应理解可将本发明用于各种其它组合、改变和环境中,能够在本文所述的本发明范围之内、在上述内容的等价内容之内和/或在相关领域的技术或知识范围内对其进行改变和修改。上文所述的实施方式是用来进一步解释已知的实施本发明的最佳实施方式,使得本领域的技术人员能够在这些或其它实施方式中应用本发明,并且根据本发明的特定应用或用途对其进行各种修改。因此,本发明并不限于所公开的内容。同样,同样地,应理解附加的权利要求书也包括作为替代的实施方式。
Claims (11)
1.一种不含链烷醇胺的组合物,所述组合物包含:
a)25-75重量%的至少一种胺,它选自氨基烷基吗啉和氨基烷基哌嗪,所述烷基是具有1-8个碳原子的直链或支链未取代的烷基;
b)10-25重量%的羟胺;
c)0-32重量%的有机稀释剂;
d)10-30重量%的水;
e)1-25重量%的腐蚀抑制剂;
所述组合物的pH大于7。
2.如权利要求1所述的组合物,其特征在于,组分a)是氨基烷基吗啉,所述烷基是具有1-8个碳原子的直链或支链未取代的烷基。
3.如权利要求1所述的组合物,其特征在于,组分a)是氨基丙基吗啉。
4.如权利要求1所述的组合物,其特征在于,所述有机稀释剂包含可与水互溶的醇。
5.如权利要求4所述的组合物,其特征在于,所述的醇由以下化学式中的至少一个表示:
R11-(CHOH)n-R12;
R11-(CHOH)n-R12-(CHOH)m-R13;
R11-(CHOH)n(CR12OH)mR13
式中
n为1-20的整数
m为1-20的整数,
R11、R12和R13各自独立地为H、烷基、芳基或烷氧基。
6.如权利要求4所述的组合物,其特征在于,所述的醇包括以下醇类中的至少一种:丙二醇、二缩三丙二醇甲基醚、1,4-丁二醇、丙二醇丙醚、二甘醇正丁醚、和四氢糠醇。
7.如权利要求1所述的组合物,其特征在于,所述腐蚀抑制剂包含选自以下化合物的至少一种:邻苯二酚、4-甲基邻苯二酚、富马酸、五倍子酸和连苯三酚。
8.如权利要求1所述的组合物,其pH为7.5-13。
9.如权利要求1所述的组合物,其特征在于所述有机稀释剂包括至少一种选自己氧基丙基胺、聚(氧乙烯)二胺及其混合物的化合物。
10.一种从基片上除去蚀刻后残余物、残留光刻胶和/或光刻胶副产物的方法,包括使其上带有蚀刻残余物、残留光刻胶和光刻胶副产物中至少一种的基片与一种不含链烷醇胺的组合物接触,所述组合物包含:
a)25-75重量%的至少一种胺,它选自氨基烷基吗啉和氨基烷基哌嗪,所述烷基是具有1-8个碳原子的直链或支链未取代的烷基;
b)10-25重量%的羟胺;
c)0-32重量%的有机稀释剂;
d)10-30重量%的水;
e)1-25重量%的腐蚀抑制剂;
所述组合物的pH大于7。
11.一种从基片上除去光刻胶的方法,该方法包括使其上带有光刻胶的基片与不含链烷醇胺的组合物接触,所述组合物包含:
a)25-75重量%的胺,它选自氨基烷基吗啉和氨基烷基哌嗪,所述烷基是具有1-8个碳原子的直链或支链未取代的烷基;
b)10-25重量%的羟胺;
c)0-32重量%的有机稀释剂;
d)10-30重量%的水;
e)1-25重量%的缓蚀剂;
所述组合物的pH大于7。
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2004
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- 2004-05-20 TW TW093114257A patent/TWI322466B/zh not_active IP Right Cessation
- 2004-05-24 KR KR1020057022394A patent/KR101153692B1/ko active IP Right Grant
- 2004-05-24 CN CN2010102517669A patent/CN101916052A/zh active Pending
- 2004-05-24 EP EP04753146.2A patent/EP1627259B1/en not_active Expired - Lifetime
- 2004-05-24 WO PCT/US2004/016270 patent/WO2004107056A1/en active Application Filing
- 2004-05-24 CN CN2004800184391A patent/CN1813223B/zh not_active Expired - Fee Related
- 2004-05-24 JP JP2006533352A patent/JP4469854B2/ja not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
---|---|
JP2007531902A (ja) | 2007-11-08 |
CN101916052A (zh) | 2010-12-15 |
TWI322466B (en) | 2010-03-21 |
WO2004107056B1 (en) | 2005-02-17 |
EP1627259A4 (en) | 2009-04-01 |
US20040234904A1 (en) | 2004-11-25 |
TW200509237A (en) | 2005-03-01 |
CN1813223A (zh) | 2006-08-02 |
KR101153692B1 (ko) | 2012-06-18 |
WO2004107056A1 (en) | 2004-12-09 |
KR20060014059A (ko) | 2006-02-14 |
MY137363A (en) | 2009-01-30 |
EP1627259A1 (en) | 2006-02-22 |
EP1627259B1 (en) | 2015-07-01 |
US6951710B2 (en) | 2005-10-04 |
JP4469854B2 (ja) | 2010-06-02 |
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