CN102652350A - 从用于等离子体室内的上部电极清除金属污染物的方法 - Google Patents
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Abstract
一种从用于等离子体室内的上部电极清除金属污染物的方法。该方法包括在浓缩的氢氧化铵、过氧化氢和水组成的清洁溶液内浸泡上部电极的步骤。该清洁溶液内不含氢氟酸和盐酸。该方法还包括可选的步骤，即在稀硝酸内浸泡上部电极并冲洗已清洁过的上部电极。
Description
本申请根据U.S.C.§119主张2009年12月18日提交的名称为METHODOLOGY FOR CLEANING OF SURFACE METALCONTAMINATION FROM AN UPPER ELECTRODE USED IN APLASMACHAMBER,美国临时申请号为61/288,087的优先权，通过引用将该临时申请的整体内容并入本申请中。
背景技术
在电容耦合等离子体（CCP）室内，集成电路由形成有图案化的微电子层的晶片或者基板制成。在基板的处理过程中，等离子体在上部和下部电极间产生，并且常被用来在基板上沉淀薄膜或者蚀刻薄膜的预定部分。射频（RF）利用电极运行一段时间后，室显示出蚀刻速率下降和蚀刻均质性偏离。蚀刻性能的下降由电极硅表面的形态改变和电极的等离子体裸露表面的污染引起。因此，需要一个系统的和有效的方法清洁电极和减小表面粗糙度以便电极符合表面污染物规格，提高生产产量。
发明内容
一种从用于等离子体室内的上部电极清除金属污染物的方法，该方法包括在氢氧化铵，过氧化氢和水组成的清洁溶液内浸泡所述整个上部电极，优选体积比从1-2:1-2:2到1-2:1-2:20的基于NH3的28-30wt%的浓缩的氢氧化铵水溶液、29-31wt％的过氧化氢水溶液和水。
附图说明
图1为根据一个实施例说明清洁上部电极的典型步骤的流程图。
图2为根据另外一个实施例清洁上部电极的设备（fixture）的剖视示意图。
图3A为图2中设备的透视视图。
图3B为图3A中B部分放大的剖视示意图。
具体实施方式
典型的电容耦合等离子体（CCP）室可以包括：室壁；有下部等离子体暴露表面的上部电极；基板支承件；嵌入在基板支承件和在基板处理过程中有效控制基板的静电夹头。室壁优选包括基板传送槽或者门，用来传送基板进出室。室壁可以可选地涂覆合适的耐磨损材料。为了提供接地电路，室壁要由金属组成，例如铝，并且电接地。基板支承件可以包括铝板，该铝板充当下部电极，并且被耦合到RF电源（通常经由匹配网络）。上部电极可以被耦合到RF电源（通常经由匹配网络）和一个或者更多的用于供应处理气体的气体管线。其他类型的电路装置可以被用来给上部电极和下部电极供应电源。例如，上部电极可以接地为供应到下部电极的电源提供回路。可替代地，下部电极可以耦合到两个或者更多的有不同的频率的RF电源。上部电极和下部电极被隔开，在它们之间形成用于生产等离子体的空间。在操作过程中，上部电极和/或下部电极通过通电将处理气体激发成等离子体状态。
上部电极可以是单片电极或者多片电极。例如，上部电极可以包括单片电路网状电极，或者可以包括内部网状电极板和形成环形外部电极环的一个或多个片段。上部电极优选包括衬垫构件，例如，铝或者石墨的垫板。单片电路网状电极或者内部网状电极板和外部电极环可以可选地用粘接材料，例如弹性体粘接材料（弹性接头），粘接到衬垫构件上。在上部电极运用弹性体粘接材料的详情公开在共同转让的美国专利号6,376,385,6,194,322,6,148,765,6,073,577中，所有这些专利的全部内容通过引用并入本申请中。弹性接头使得在电极和衬垫构件间能运动，以补偿上部电极温度循环引起的热膨胀。弹性接头可以包括电的和/或热的导电填料和在高温下稳定的催化剂固化的聚合物。例如，弹性接头可以由硅酮聚合物形成，填料可以由铝合金或者硅粉形成。为了提供低电阻和减少电极污染，上部电极优选由单晶硅形成。衬垫构件、弹性接头和网状电极可以包括多个孔或者气体出口，使得处理气体能通过上部电极。优选地，上部电极的孔的直径从600μm到1000μm。
在等离子体处理过程中，上部电极可以被诸如Ca,Cr,Co,Cu,Fe,Li,Mg,Mo,Ni,K,Na,Ti,Zn之类金属污染（例如，从上部电极下的基板处理）。在等离子体处理过程中，这些金属可以从上部电极释放出来，同时污染正在进行例如等离子体蚀刻之类处理的基板，。
为了阻止经处理的基板的金属污染，上部电极优选在一定数量的RF时间之后定期地从室内拿出并且进行清洁。可替代地，此处描述的清洁可以作为新的上部电极的最后生产阶段被实施。图1显示了说明根据一个实施例清洁上部电极的典型步骤的流程图100。在步骤101中，上部电极被浸泡在异丙醇（IPA）内一段合适的时间，例如10分钟至1小时，优选大约30分钟，以从上部电极移除有机的污染物。此处所使用的“大约”指±10%。
在步骤102，上部电极用清洁室的擦布（例如VWR LabShop生产的，由带有密封边和耐洗的针织聚酯组成的100级耐酸的清洁室擦布(Batavia,Ill.)）擦拭，然后用去离子水（DIW）冲洗一段合适的时间，例如1至10分钟，优选约2分钟。图2是设备208的剖视示意图，在此设备上可以擦拭上部电极300。图3A为用来支承上部电极300的设备208的透视图，图3B为图3A中B部分放大的剖视示意图。擦拭工具200优选由
（聚四氟乙烯）组成并且包括把手部分202和截头圆锥体部分203。截头圆锥体部分203有覆盖了擦布206的平面204，擦布在擦拭过程中可以被例如EPA之类的清洁溶液润湿。擦拭工具200的人类操作者优选握住把手部分202，施加向上的力210使擦拭工具200的向上的平面与上部电极300（例如等离子体裸露表面）的向下的表面相接触。进一步，设备208在擦拭过程中可以旋转。
如图2，3A和3B所示，与根据待被清洁的上部电极300的尺寸设置的设备208，有坚固的基础结构和三个或者更多的垂直支承构件来支承上部电极300，以便上部电极300的等离子体暴露表面朝下面。每个支承构件的顶部优选有内部台阶，上部电极300的边缘可以停靠在该台阶上面。在等离子体暴露表面的清洁过程中，这些台阶可以防止上部电极300从支承构件上滑落。支承构件和底部优选涂上耐化学物质或者由耐化学物质组成，例如
在步骤103，优选在室温下，将上部电极浸泡在清洁溶液中一段合适的时间，例如10到60分钟。此清洁溶液通过混合氢氧化铵、过氧化氢和水制成，其中优选浓缩的氢氧化铵水溶液（CAS#1336-21-6）（28-30wt%的NH3，优选29-31wt%）、过氧化氢水溶液（CAS#7722-84-1）和水，体积比为1-2:1-2:2到1-2:1-2:20，优选1-2:1-2:2到1-2:1-2:15，更优选1:1:2到1:1:10，最优选1:1:10。
清洁溶液中的过氧化氢可以分解为水和原子氧。原子氧氧化上部电极上的金属污染物。清洁溶液中的铵离子可以螯合氧化的金属污染物并且形成可溶性复合物。例如，铜污染物与清洁溶液反应如下：Cu+H2O2=CuO+H2O；CuO+4NH3+H2O=Cu(NH3)4 2++2OH-。
在步骤104，上部电极用去离子水冲洗合适的时间，例如大约5分钟，以移除清洁溶液的任何残留。
在步骤105，上部电极（前面和后面）用去离子水浸泡的清洁室的擦布擦拭合适的时间，例如1至10分钟，优选大约2分钟。
在可选步骤106，上部电极被浸泡在稀硝酸溶液(CAS#7697-37-2)(1-5wt%,优选2wt%)内合适的时间，例如1至10分钟，优选2至5分钟。稀硝酸能够进一步有效地从上部电极移除金属污染物。
如果可选步骤107被实行，随后实施108步骤，用去离子水冲洗上部电极合适的时间，例如1至10分钟，优选大约5分钟，以移除稀硝酸的任何残留。
步骤101至108可以被重复一次或者更多次。
在步骤109，上部电极被移到100级或者更好的清洁室。
在步骤110，用超纯水冲洗上部电极一段合适的时间，例如1至30分钟，优选大约10分钟。
该清洁过程之后可以进行其他传统的清洁步骤。
上部电极的清洁过程没有应用带有氢氟酸的机械抛光或者处理，因此防止了弹性接头的过度磨损和损坏。此清洁过程有效地从易进入表面和其他表面，例如螺丝孔，气体通道等的表面，移除铜和其他金属污染物。
表1
表1显示的是硅质网状电极的等离子体暴露表面清洁前后的元素成分分析。
人类操作者在执行本处描述的清洁过程和在步骤之间处理上部电极的执行过程中优选戴上手套，以避免接触到有机污染物。另外，如有必要，人类操作者可以戴上新的手套，以避免在一个步骤中产生的污染物和原子转移到随后的步骤中的上部电极上。
虽然该清洁方法和该清洁溶液参照本发明的具体实施例进行了详细描述，但是对于本领域技术人员而言，显而易见，可以进行各种改变和修改，以及使用等同的方式，而不脱离所附权利要求的范围。
Claims (21)
1.一种从用于等离子体室内的上部电极清除金属污染物的方法，包括：将整个所述上部电极浸泡在由氢氧化铵、过氧化氢和水组成的清洁溶液内。
2.如权利要求1所述的方法，其中所述上部电极在所述清洁溶液中浸泡10至60分钟。
3.如权利要求1所述的方法，进一步包括：
在所述清洁溶液内浸泡之前，
将所述上部电极浸泡在异丙醇内约30分钟；
用清洁室的擦布擦拭所述上部电极和用去离子水冲洗所述上部电极约2分钟；以及
在所述清洁溶液内浸泡之后，
用去离子水冲洗上部电极约5分钟；
用清洁室的擦布并使用去离子水擦拭上部电极约2分钟；
可选地，将所述上部电极浸泡在浓度为2%的硝酸溶液内2至5分钟，用去离子水冲洗上部电极约1至10分钟。
4.如权利要求3所述的方法，进一步包括重复所述步骤至少一次，接着用超纯水冲洗所述上部电极约1至30分钟。
5.如权利要求1所述的方法，其中所述清洁溶液按照以下方式被配制，将基于NH3的28-30wt%的浓缩的氢氧化铵水溶液、29-31wt%的过氧化氢水溶液和水，按照氢氧化铵:过氧化氢:水为1-2:1-2:2到1-2:1-2:20之间的体积比混合。
6.如权利要求5所述的方法，其中所述体积比在1:1:2到1:1:10之间。
7.如权利要求1所述的方法，其中所述上部电极包括单晶硅的网状电极。
8.如权利要求1所述的方法，其中所述清洁溶液内不含氢氟酸和盐酸。
9.如权利要求1所述的方法，其中在不抛光所述上部电极的等离子体暴露表面的情况下进行清洁。
10.如权利要求1所述的方法，其中所述清洁要在10000级或者更好的清洁室内进行。
11.如权利要求1所述的方法，其中所述上部电极包括通过弹性接头连接到硅网状电极上的铝或者石墨衬垫构件。
12.如权利要求1所述的方法，进一步包括在清洁之前从等离子体室拆除所述上部电极并在相同或者不同的室中重新安装已清洁的所述上部电极。
13.如权利要求1所述的方法，其中所述清洁溶液将铜污染物从3000x1010个原子/cm2之上降低到不到50x1010个原子/cm2。
14.如权利要求1所述的方法，其中所述清洁溶液将镍污染物从200x1010个原子/cm2之上降低到不到5x1010个原子/cm2。
15.如权利要求1所述的方法，其中所述清洁溶液将锌污染物从250x1010个原子/cm2之上降低到不到75x1010个原子/cm2。
16.如权利要求1所述的方法，其中所述清洁溶液将铁污染物从50x1010个原子/cm2之上降低到不到5x1010个原子/cm2。
17.如权利要求1所述的方法，其中所述清洁溶液将钙污染物从700x1010个原子/cm2之上降低到不到400x1010个原子/cm2。
18.如权利要求1所述的方法，其中所述清洁溶液将镁污染物从50x1010个原子/cm2之上降低到不到20x1010个原子/cm2。
19.如权利要求1所述的方法，其中所述清洁溶液将钾污染物从450x1010个原子/cm2之上降低到不到5x1010个原子/cm2。
20.如权利要求1所述的方法，其中所述清洁溶液将钠污染物从1500x1010个原子/cm2之上降低到不到50x1010个原子/cm2。
21.如权利要求1所述的方法，其中所述清洁溶液将钛污染物从250x1010个原子/cm2之上降低到不到75x1010个原子/cm2。
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| US20190341276A1 (en) * | 2018-05-03 | 2019-11-07 | Applied Materials, Inc. | Integrated semiconductor part cleaning system |
| CN110528010B (zh) * | 2019-09-20 | 2020-11-03 | 北京航空航天大学 | 一种镍基高温合金断口清洗方法 |
| KR102654366B1 (ko) * | 2024-03-06 | 2024-04-03 | 주식회사 디에프텍 | 반도체 제조공정에 사용되는 샤워헤드 세정 방법 |
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| WO2011084127A3 (en) | 2011-10-13 |
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