CN1052706A - 使用卤化物的铜蚀刻方法 - Google Patents
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Abstract
本发明公开了一种可用于集成电路制作的铜层
蚀刻的蚀刻方法，该方法使用了卤化物与铜反应，最
好使用高强的紫外光的光激能和光定向辅助，以生成
或具挥发性的、或易用溶液清洗的产物。本方法为各
向异性的。
Description
本发明涉及铜镀层的蚀刻方法和设备，尤其涉及在铜镀层上镀敷有第二种涂层材料的铜镀层的蚀刻方法和设备。这样的铜镀层有如印刷电路制作中使用光形成和光激活的卤素基团蚀刻所得的铜镀层，用于印刷电路制作的和集成电路金属镀敷层的底版铜镀层。
相当厚的铜镀层或较薄的底层铜镀层上的图案，一直是印刷电路制作技术中所须要的。近来，在集成电路的制作技术中希望能在薄的铜层上形成图案。铝已被成功地普遍用于集成电路技术，从而在集成电路的活性元件之间，或跨越其上而形成导通线路。其部分原因是，人们认识到可以用一些技术容易地在铝上形成图案。但是，正如胡等人在“用于铜的扩散屏障的研究”（1986）IEEE.V-MICConference 1986年6月号9-10，181-187页中所论述的，在集成电路中，铜具有许多优于铝金属镀敷层的长处，如：较高的导电性，更好的电迁移阻力，以及较小的能耗。然而，又如该文进一步论述的，铜也比铝能更易扩散入硅中。不过，此问题已由在硅和集成电路的其它镀敷层以及铜金属镀敷层之间使用一扩散屏障而得以满意地解决。
现有的铜膜的图形蚀刻如下完成：在印刷电路的制作中，以湿法加工;其中，先把一种起保护作用的、具图形的基本膜，如光敏抗蚀膜施于铜镀层之上;然后，用一种强液体蚀刻剂-通常是一种酸，腐蚀暴露的铜直至基片材料。这种方法在用于集成电路的制作中尚存在以下的问题。由于蚀刻中的杂质可能被带入集成电路片中，因而此湿式加工一开始即是“脏”的;所需的湿蚀刻剂常因与人体的接触或吸入由此所产生的气体，而易对操作者产生危害;铜的蚀刻需蚀刻剂和高温，而此二者都可能破坏集成电路中的其它涂敷层;铜的湿式蚀刻是呈各向同的性质，这样使得对VLSI电路的铜金属镀敷非常困难，而湿式蚀刻的废品弃置又使其费用昂贵。
因此，由于在集成电路中使用铜金属层镀敷的要求日益增加，和现有的湿式蚀刻技术中存在的固有的问题，开发一种用于铜镀层，尤其是用于集成电路制作的铜镀层的蚀刻的更有效的蚀刻方法和设备，已显得越加重要。
阴极真空喷镀技术现用于从涂铜的铝膜上除去铜，因而，它可能应用于除去铜膜。不过，即然，铜没有被转化为一种挥发性形态，则阴极真空喷镀，由高能级离子碰撞所引起的铜原子及铜原子团的物理学移动，将不会显示出各种薄膜的选择性的清除，而导致在反应室中产生高度的沉淀物的累积。另外，阴极真空喷镀清洗技术相对来说，速度较慢，难于控制，并对掩蔽层的选择性不够。
干式蚀刻方法包括一个可形成活性剂的等离子体，如卤素、胺、或一种有机基团。它和铜反应并形成铜的挥发性生成物。干式蚀刻方法接近于一种有效的铜蚀刻方法，它解决了在其它方法中所碰到的，特别是在反应室中的沉淀物的再次淀积的一些问题。但是，基于可能形成的铜化合物具有已知的高熔点和沸点，再联系到与这些等离子体工艺有关的基体的温度的正常范围，一般认为，铜不会发生挥发。这样，这些加工方法将不会是成功的。更进一步，等离子体的发射产生一个很宽范围的离解的反应性产物，这些产物可以以匀相的或非匀相地结合以形成聚合物残留物。例如碳氢化合物和炭氯化合物会生成含很多粒子的聚合物残渣。同样，如果这些方法所产生的反应生成物不是挥发性的，一般认为，其表面的反应将阻止其表面之下的铜块材料的进一步反应发生。如W.Sesselmann等人在“氯和铜的相互作用”Surface Seiences，（1986）176卷32-90页中所论述的。他们已对铜和氯的反应作了一些研究，一些较早的对铜膜的离子蚀刻法所作的一些研究，见述于Schwartz等人的“铜膜的反应性离子蚀刻法”，Journal of the Electochemical Society，V01.130，No.8（1983），1777-1779页。
本发明者发现：用由光产生、激活或赋于能量，并暴露于铜膜的卤素离子的干式或干/湿式方法，可以在即使集成电路制作的场合下，有效地蚀刻铜金属镀敷层。
本发明者又发现：特别在较高的基片的温度或反应室温度下，铜卤化物的反应产物从未屏蔽区域作各向异性挥发是可能的。而且，即使当该铜的卤化物产物不是挥发性的，整体铜膜与卤素离子的完全反应可以以定向性地、或各向异性地发生，以产生一个易由溶剂洗涤或用水洗来非均质地去除的铜的卤化物反应物。在以上二种情况下，反应生成物可被非均质地清除。
因此，本发明的目的之一在于，提供一种铜膜的蚀刻方法，该铜膜可用于集成电路的制作。
本发明的又一目的在于，提供一个在铜蚀刻的方法中的图案成形的临界尺寸界限和控制。
本发明的目的之一在于，提供一种无需强的湿式蚀刻剂的铜膜蚀刻方法。
本发明的又一目的在于，提供一种各向异性的，可用于集成电路制作的铜蚀刻方法。
本发明的目的也在于，提供了一个用于经光诱导生成的基团使定向地透过铜层扩散。
本发明的目的还在于，提供一种铜膜蚀刻方法，该方法避免了由阴极真空喷镀技术产生的工艺室的污染。
本发明的目的还在于，提供一种实质上是干式的铜的蚀刻方法。参照附图及下述实施例的详细描述，这些及其它本发明的优点对一普通技术人员来说将是显而易见的。
图1根据本发明，为用于本发明的方法中的反应室实施例的结构图。
图2a和2b根据本发明，为在本蚀刻工艺的二阶段中，半导体片的电子显微镜下的二个侧视图。
参照图1，图中显示了一个封闭小室6，它具有基片座8，基片座8通常具有可调节温度的加热元件（图中未示）以加热置于其上的基片。基片座8上所示为一个典型的带有基片9的集成电路片。例如一个单晶硅基片，一个铜金属镀层10以及一个形成图案的屏框掩蔽模板11，（并不按尺寸比例绘制）。屏框掩蔽模板11在集成电路的制作工艺中，为一已知类型的光敏屏蔽材料。它可根据公知的照相平版印刷技术形成图案并被蚀刻。但是，除了照相平版、屏蔽模板11也可由其它技术制作。基片座8可以包括调节的加热元件（图中未示）。以加热基片9至所需的工艺温度。此工艺温度可依各种因素决定。如需得到此结合的铜生成物的高度的或完全的挥发，则需高的工艺温度。所需高温具体数值可依据所用的游离基反应剂而定。不过，影响使用如此高的工艺温度的因素在于，所加工的集成电路片可能由于挥发反应所用的有效温度而遭遇损坏或破坏。当然，印刷电路基片可能并不会因此高的工艺温度而被损坏。
参照图1，一个高强光源4，如经过滤的紫外光源，一个1000瓦的汞/氙灯置于工艺室6之上。聚焦元件2和4被对准地置于穿过透明窗7的高强光下。7可以是一种石英窗，将光照在带有屏蔽模板的铜镀层10和11之表面上。透明窗7为封闭的，譬如用“O”型环14封闭。要指出的是，尽管图1显示了此高强光直接垂直照射于该电路片，但已发现，如果该工艺室的放置使该光线与电路片成其它角度或平行，则该高强光的照射同样有效。
具有带阀门13的进口部分12，可使反应剂R进入室6并和薄片9、10和11接触。反应剂R为氯、氟、溴或碘游离基的卤素。此卤素游离基可从卤素化合物获得。例如，CF4正如本领域已熟知的那样，用光化学解离，微波余辉解离法或等离子体放电解离等得到。另外，也可在该工艺室内，以光化学解离方法，用如从源4引入Cl2至高强紫外光5下而获得该卤素游离基团。该卤素游离基团R可由高强光线5被作光激活，同时与该铜镀层10和屏蔽模板层11接触。
使用了可被光激活的卤素游离基团R，在室6内发生的蚀刻过程，将依最初发生反应时的温度和所用的蚀刻剂而按两套不同的方法发生。当铜层10与光激活反应物R＊接触，该铜和卤素的原子在表面发生反应，形成一个铜的卤化合物。这些反应可表示如下：
Ⅰ.游离基团的形成
这里，P为母体分子，R为胺或有机游离基团，R＊为光激活的游离基团。
Ⅱ.与铜结合的游离基团的形成
这里，（g）为气体，（s）为固体。
Ⅲ.CuR的除去
，这里，S为溶剂，（Soln）为溶液，（ads）为被吸收。
如果在反应条件下，CuR是挥发性的，则生成物CuR被作为蒸汽放出，并可作为汽体泵出室6。
如果CuR不是挥发性的，此生成物滞留在铜层表面上。然而，本发明者惊奇地发现：此时反应仍在铜层整个表面连续进行而形成CuR。在已述的工艺条件下，该表面反应并不阻止在表面之下的反应发生。当这样的反应在整个铜层10表面发生之后，产生的铜卤化产物CuR可用适当的溶液，如水或丙酮被清洗去。而且，可以相信，R的再次扩散入CuR中和铜发生反应为一种光敏的定向性扩散。
图2a和2b是在电子显微镜下所观察到的，在本发明的方法中的二阶段中使用了铜镀层的集成电路片的示意图。图2a的薄片表示蚀刻之前，显示了一个硅基片9，一个二氧化硅层9a，一个钨钛阻挡层10a和一个铜层10。
此处用到一个屏蔽模板11，并由如已知的照相平板印刷方法，或其它已知手段在其上施以图案。这时，用图象反转显影方法产生一个悬臂状抗蚀刻的悬突体。
图2b描述了在下述条件下，在图1中的室内完成蚀刻过程之后的同样的薄片。这些薄片（9、10和11）可用稀释硝酸去光。一支1000瓦的带水滤器的汞一氙灯被定向照在片9、10和11之上。该水滤清器用作当通过深度紫外光时，除去高于1.3μ的大多数红外光，使降至大约200nm。该光线垂直射于薄片上。这些薄片被加热至200℃。氯分子Cl2，在10乇压力下，以100sccm之比率引入该室。氯分子Cl2被该光源的光能作光离解，产生Cl离子游离基。该片暴露于氯游离基10分钟。在这之后，图2b又显示了未被掩蔽的整个铜层发生反应，其厚度扩展为原来厚度的3倍。产生的层膜12即为CuCl2。另由于初始防蚀面，可以看到一个空隙14。一般的洗涤可清洗此产生的薄膜。以丙酮或水洗通常可洗去反应生成物。注意，当抗蚀剂接触铜膜表面时，该铜层侧面并未被蚀刻。
要指出的是，本发明虽揭示了有关实施例，但它们并未被限定。这些实施例中所得出的数据可在一定的范围内变化，以获所需的结果。因而，本发明的范围只在所附的权利要求书和相应的修改中才被限定。
Claims (6)
1、一种在密闭的小室内对基片上的铜层作各向导性蚀刻，以形成具图案的导体的蚀刻方法，它包括以下步骤：
对所说的铜层的不企图被蚀刻的区域作屏框掩蔽；
在密闭小室中引进卤素游离基团至所说的铜层上，以在所说的卤素游离基团被高强光照射后，形成一铜卤化物的反应产物。
2、如权利要求1所述的方法，其特征在于，它进一步包括如下步骤：
加热所说的基片至一温度，在此温度下，所说的铜的卤化物反应产物能大体上挥发。
3、如权利要求1所述的方法，其特征在于，它进一步包括如下步骤：
清洗所说的基片，以去除所说的铜的卤化物反应产物。
4、如权利要求2所述的方法，其特征在于，所说的基片被加热至2000℃以上。
5、如权利要求1所述的方法，其特征在于，所述的卤素游离基团为氯游离基团。
6、如权利要求1所述的方法，其特征在于，所说的高强光为紫外光。
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| US45354989A | 1989-12-20 | 1989-12-20 | |
| US453,549 | 1989-12-20 |
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| CN1052706A true CN1052706A (zh) | 1991-07-03 |
| CN1025508C CN1025508C (zh) | 1994-07-20 |
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| CN90110066A Expired - Fee Related CN1025508C (zh) | 1989-12-20 | 1990-12-20 | 使用卤化物的铜蚀刻方法 |
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| EP (1) | EP0433983B1 (zh) |
| JP (1) | JP3105547B2 (zh) |
| KR (1) | KR100221992B1 (zh) |
| CN (1) | CN1025508C (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104953027A (zh) * | 2014-03-27 | 2015-09-30 | 朗姆研究公司 | 蚀刻非挥发性金属材料的方法 |
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| MX9305898A (es) * | 1992-10-30 | 1995-01-31 | Texas Instruments Inc | Metodo de grabado fotoquimico anisotropico para la fabricacion decircuitos integrados. |
| JPH06326059A (ja) * | 1993-05-17 | 1994-11-25 | Fujitsu Ltd | 銅薄膜のエッチング方法 |
| JP2793472B2 (ja) * | 1993-06-24 | 1998-09-03 | 日本電気株式会社 | 銅微細加工方法および銅微細加工装置 |
| JPH0729908A (ja) * | 1993-07-15 | 1995-01-31 | Nec Corp | 銅微細配線の形成方法 |
| US7829552B2 (en) | 2003-11-19 | 2010-11-09 | Metabasis Therapeutics, Inc. | Phosphorus-containing thyromimetics |
| EA020466B1 (ru) | 2007-06-04 | 2014-11-28 | Синерджи Фармасьютикалз Инк. | Агонисты гуанилатциклазы, пригодные для лечения желудочно-кишечных нарушений, воспаления, рака и других заболеваний |
| US8969514B2 (en) | 2007-06-04 | 2015-03-03 | Synergy Pharmaceuticals, Inc. | Agonists of guanylate cyclase useful for the treatment of hypercholesterolemia, atherosclerosis, coronary heart disease, gallstone, obesity and other cardiovascular diseases |
| CA2726917C (en) | 2008-06-04 | 2018-06-26 | Synergy Pharmaceuticals Inc. | Agonists of guanylate cyclase useful for the treatment of gastrointestinal disorders, inflammation, cancer and other disorders |
| CA2730603C (en) | 2008-07-16 | 2019-09-24 | Synergy Pharmaceuticals Inc. | Agonists of guanylate cyclase useful for the treatment of gastrointestinal disorders, inflammation, cancer and other disorders |
| WO2010093601A1 (en) | 2009-02-10 | 2010-08-19 | Metabasis Therapeutics, Inc. | Novel sulfonic acid-containing thyromimetics, and methods for their use |
| US9616097B2 (en) | 2010-09-15 | 2017-04-11 | Synergy Pharmaceuticals, Inc. | Formulations of guanylate cyclase C agonists and methods of use |
| EP2970384A1 (en) | 2013-03-15 | 2016-01-20 | Synergy Pharmaceuticals Inc. | Agonists of guanylate cyclase and their uses |
| CA2905435A1 (en) | 2013-03-15 | 2014-09-25 | Synergy Pharmaceuticals Inc. | Compositions useful for the treatment of gastrointestinal disorders |
| CN113388007A (zh) | 2013-06-05 | 2021-09-14 | 博士医疗爱尔兰有限公司 | 鸟苷酸环化酶c的超纯激动剂、制备和使用所述激动剂的方法 |
| WO2015012205A1 (ja) | 2013-07-23 | 2015-01-29 | 第一三共株式会社 | 高血圧症の予防又は治療のための医薬 |
| JP6934859B2 (ja) | 2016-03-24 | 2021-09-15 | 第一三共株式会社 | 腎疾患の治療のための医薬 |
| US10177002B2 (en) * | 2016-04-29 | 2019-01-08 | Applied Materials, Inc. | Methods for chemical etching of silicon |
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| JPS6175529A (ja) * | 1984-09-21 | 1986-04-17 | Toshiba Corp | ドライエツチング方法及び装置 |
| US4622095A (en) * | 1985-10-18 | 1986-11-11 | Ibm Corporation | Laser stimulated halogen gas etching of metal substrates |
| JPH01215986A (ja) * | 1988-02-24 | 1989-08-29 | Hitachi Ltd | ドライエッチング方法 |
-
1990
- 1990-12-18 EP EP90124588A patent/EP0433983B1/en not_active Expired - Lifetime
- 1990-12-18 DE DE69032089T patent/DE69032089T2/de not_active Expired - Fee Related
- 1990-12-19 KR KR1019900021074A patent/KR100221992B1/ko not_active IP Right Cessation
- 1990-12-20 CN CN90110066A patent/CN1025508C/zh not_active Expired - Fee Related
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104953027A (zh) * | 2014-03-27 | 2015-09-30 | 朗姆研究公司 | 蚀刻非挥发性金属材料的方法 |
| CN104953027B (zh) * | 2014-03-27 | 2018-05-22 | 朗姆研究公司 | 蚀刻非挥发性金属材料的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69032089D1 (de) | 1998-04-09 |
| EP0433983B1 (en) | 1998-03-04 |
| JPH04159718A (ja) | 1992-06-02 |
| EP0433983A3 (en) | 1993-02-24 |
| DE69032089T2 (de) | 1998-06-25 |
| JP3105547B2 (ja) | 2000-11-06 |
| EP0433983A2 (en) | 1991-06-26 |
| KR910013442A (ko) | 1991-08-08 |
| CN1025508C (zh) | 1994-07-20 |
| KR100221992B1 (ko) | 1999-09-15 |
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