CN100357493C - 半导体加工设备的防腐组件及其制造方法 - Google Patents

半导体加工设备的防腐组件及其制造方法 Download PDF

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CN100357493C
CN100357493C CNB008095914A CN00809591A CN100357493C CN 100357493 C CN100357493 C CN 100357493C CN B008095914 A CNB008095914 A CN B008095914A CN 00809591 A CN00809591 A CN 00809591A CN 100357493 C CN100357493 C CN 100357493C
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R·J·斯泰戈
C·张
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Abstract

半导体加工设备的防腐组件如等离子体腔室，其包括如铝或铝合金、不锈钢或耐火金属的金属表面，该金属表面上镀有磷镍镀层和如氧化铝、碳化硅、氮化硅、碳化硼或氮化铝的外陶瓷镀层。该磷镍镀层可通过化学镀被沉积，而陶瓷镀层可通过热喷镀沉积。为了增加陶瓷镀层的粘附力，在沉积陶瓷镀层前，可先对磷镍镀层进行糙化处理。

Description

半导体加工设备的防腐组件及其制造方法
                       发明背景
                       发明领域
本发明涉及半导体加工设备和提高其组件防腐性能的方法。
                     相关技术描述
在半导体加工领域，真空加工腔室常被用于蚀刻和在基片上化学气相沉积(CVD)物质，该化学气相沉积物质是通过向真空腔室内充入蚀刻或沉积气体，并向该气体施加RF场以使其激化到等离子态而进行的。在美国专利4,340,462；4,948,458；5,200,232和5,820,723中公开了平行板、变压器偶合等离子体(TCPTM)(又称为感应耦合等离子体(ICP))和电子回旋共振(ECR)反应器及其组件的例子。由于这些反应器中的等离子体环境的腐蚀性和对最小的微粒和/或重金属污染的要求，所以就非常需要该设备的组件具有良好的防腐性能。
在半导体基片的加工中，一般用如机械夹具或静电夹具(ESC)的基片夹具将基片固定在真空腔室中。这些夹具系统和其组件的实例在美国专利5,262,029和5,838,529中可以看到。工作气体可以通过如气嘴、气环、气体分配盘等不同方式被输入到所述腔室中。例如在美国专利5,863,376中，可发现感应偶合等离子体反应器及其组件用的是温控气体分配盘。除等离子体腔室设备外，其它用于加工半导体基片的设备包括传输机构、供气系统、衬套、起落机构、装料控制、门机构、机械手、固定装置等。这种设备的组件处于与半导体加工相关的不同腐蚀性条件下。而且如硅晶片的半导体基片的加工和如用于平板显示器的玻璃基片的介电材料的加工都要求很高的纯度，在这样的环境中就非常需要组件具有改进的防腐性能。
铝和铝合金通常被有于等离子体反应器的器壁、电极、基座、固定装置和其它组件。为了防止这种金属组件的腐蚀，人们应用了各种技术在铝表面涂覆了各种涂层。如美国专利5,641,375中公开了将铝质室壁阳极化，以降低该壁的等离子体腐蚀和磨损。’375专利指出阳极化层最后被溅射或腐蚀掉了，以至于不得不更换所述腔室。美国专利5,895,586描述了一种记载在日本申请未审公开62-103379中的在铝材上形成Al2O3、AlC、TiN、TiC、AlN等防腐膜的技术。
美国专利5,680,013提到在美国专利4,491,496中公开了一种在蚀刻室的金属表面用火焰喷镀Al2O3的技术。’013专利指出铝和陶瓷镀层(如氧化铝)之间热膨胀系数的不同导致了镀层在腐蚀性环境中由于热周期性变化而破坏和最后失效。为了保护腔室壁，美国专利5,366,585；5,798,016和5,885,356中提出了衬套装置。如’016专利公开了陶瓷、铝、钢和/或石英衬套，其中优选铝，因为铝的机械加工性能好且具有氧化铝、Sc2O3或Y2O3覆盖层，其中优选氧化铝来覆盖铝，以保护铝不受等离子体的影响。’585专利公开了一种自立式陶瓷衬套，其厚度至少0.005英寸，由固体氧化铝加工而成。’585专利还提到陶瓷层的使用，该陶瓷层是通过火焰喷镀或等离子喷镀氧化铝而沉积的，这样不会消耗位于下面的铝。’365专利公开了一种氧化铝的陶瓷衬套和一种用于保护晶片座的氮化铝陶瓷护罩。美国专利5,885,356公开了可用于CVD室的陶瓷衬套材料。
各种各样的镀层已被用于半导体加工设备的金属组件。例如，美国专利5,879,523公开了一种溅射室，其中在金属如不锈钢、铝上热喷镀了一层氧化铝，在其间具有任选的NiAlx结合镀层。美国专利5,522,932和5,891,53公开了一种用于基片的等离子加工装置的金属组件的铑镀层，在其间具有任选的镍镀层。美国专利5,680,013公开了用于等离子体加工室中的金属表面的非连接型陶瓷保护，优选的陶瓷材料是经烧结的AlN，次优选的材料包括氧化铝、氟化镁和氧化镁。美国专利5,904,778公开了在自立式SiC上的SiC CVD镀层，其可以用作室壁、室顶或环绕着晶片的环圈。
至于等离子体反应器组件如喷头气体分配系统，对于喷头的材料已经有了很多提议。如在美国专利5,569,356中公开了硅、石墨或碳化硅的喷头。美国专利5,494,713公开了在铝电极上形成耐酸铝膜，并在该耐酸铝膜上再镀一层硅膜如氧化硅或氮化硅。’713专利中提到硅镀膜的厚度应等于或小于10微米，优选约5微米，因为铝镀膜、耐酸铝镀膜和硅镀膜的线膨胀系数不同，当硅镀膜太厚时很易发生裂缝。但厚度小于5微米时不能对铝基片提供充分的保护，所以也不适宜。美国专利4,534,516公开了一种不锈钢、铝、铜等的顶置喷头电极。美国专利4,612,077公开了一种镁喷头电极。美国专利5,888,907公开了无定形碳、SiC或Al的喷头电极。美国专利5,006,220和5,022,979公开了一种喷头电极，其或全部用SiC制造，或是在碳基片上通过CVD沉积覆盖上SiC，以提供高纯度碳化硅表面层。
考虑到半导体加工设备组件对高纯度和防腐性能的要求，本技术领域内有一种改进用于这些组件的材料和/或镀层的需要。此外，对于所述腔室的材料而言，任何能提高等离子体反应器腔室寿命并因此减少设备停机的材料，都将有利于降低半导体晶片的加工费用。
                      本发明概述
本发明的第一个方面是提供了一种在半导体加工设备组件金属表面施加防腐性镀层的方法。该方法包括：(a)在组件的金属表面沉积磷镍(phosphorus nickel)镀层；和(b)在该磷镍镀层上再沉积陶瓷镀层，以形成防腐性的外表面。所述金属表面可以是经阳极化处理或未经处理过的铝、不锈钢、耐火金属(如钼)或其它用于等离子腔室的金属或合金。所述陶瓷镀层可以是氧化铝、SiC、AlN、Si3N4、BC或其它等离子体相容的陶瓷材料。
本发明的第二个方面是提供了一种金属组件。该组件包括：(a)金属表面；(b)金属表面上的磷镍镀层；(c)该磷镍镀层上的陶瓷镀层，其中氧化铝镀层构成了最外面的防腐蚀性表面。
                       附图说明
通过以下结合附图对优选实施方案的详细描述，将使本发明的目的和优点变得明显，其中：
图1是等离子体反应器腔室的剖面示意图，该腔室具有一个镀有本发明的防腐性镀层的组件。
图2是图1中A部分的防腐性镀层的详图。
          本发明优选实施方案的详细描述
本发明为半导体加工设备组件(如等离子体加工反应器腔室的部件)的金属表面提供了一种有效的防腐途径。这些组件包括室壁、基片支承、气体分配系统(包括喷头、阻气板、环气嘴等)、固定器、加热元件、等离子体隔板、衬套、传送模件组件(如机械手、紧固器、内外室壁等)等等。
尽管本发明适用于任何类型的具有金属表面的组件，但为了解释方便，本发明将参照美国专利5,820,723中所述的设备进行详细描述，该文献在此全文引作参考。
图1所示的真空加工反应器腔室10包括基片座70，它能给基片60提供一个静电夹持力，也能在基片被氦后冷却时对其提供RF偏移，限制环72能把等离子体局限在基片的上方。在反应器腔室10的顶部有一个为保持该腔室内高等离子体密度(如1011-1012个离子/cm3)的能源如天线40，其由适当的RF源驱动，以提供高密度的等离子体。该腔室包括真空泵装置，其通过腔室底中部的真空口20对该腔室抽真空，以使腔室内部30保持所需的压力(如低于50毫托，一般为1-20毫托)。
在天线40和加工腔室10的内部之间有一个厚度均一的基本上平的绝缘窗口50，它构成了加工腔室10顶部的真空壁。气体分配盘52位于窗口50之下，且其包括有如环形洞的开口，以把工作气体从供气装置输入到腔室10中。从气体分配盘延伸出一个圆锥形的衬套54，且该衬套包围着基片座70。
工作时，被加工的半导体基片如硅晶片60被固定在基片座70上，当进行氦后冷却时，一般用静电夹具74将基片固定。然后工作气体通过窗口50和气体分配盘52之间的空隙进入真空加工腔室10。在申请号为08/509,080；08/658,258和08/658,259的美国专利中公开了适合的气体分配盘的排列(如喷头)，这些文献的内容在此引作参考。例如，尽管图1中窗口和气体分配盘排列是平面的且厚度均一，但非平面和/或非均匀厚度的几何形状也能用于窗口和/或气体分配盘。通过向天线40提供合适的RF动力就能在窗口和基片之间的空隙中点燃高密度的等离子体。
暴露在等离子体中且有腐蚀现象发生的如经或未经阳极化处理的铝质壁的腔室壁28和如基片座70、固定器56、衬套54等的金属组件都是施加本发明防腐性镀层的对象，因此在等离子体腔室的操作中就不必将它们都罩起来。可被镀涂的金属和/或合金包括经或未经阳极化处理的铝及其合金、不锈钢、耐火金属(如钨、钼)及其合金、铜及其合金等等。在优选的实施方案中，被镀涂的组件是腔室壁28，它具有经或未经阳极化处理的铝表面29。本发明的镀层允许使用铝合金，而对铝合金的组成(这样除高纯度的铝外，就可以用更经济的铝合金)、颗粒结构或表面条件没有特殊要求。在下面的讨论中，如图2所示的被镀涂的组件的例子是铝质的腔室壁28，其具有磷镍镀层80和陶瓷镀层90。
根据本发明，在铝质侧壁28上镀磷镍层80可以用常规的技术来完成，包括如化学镀、电镀、喷镀、浸镀或化学气相沉积。化学镀是优选的提供P-Ni镀层的方法，其允许在没有电流的情况下对腔室复杂的内表面或其它腔室组件如气体供给组件中的气体通道等进行镀涂。在美国专利4,636,255中公开了一种化学镀P-Ni合金的技术，其内容在此引作参考。在美国金属协会1989年出版，H.Boyer和T.Gall编辑的《金属手册》(Metals Hahdbook)(第五版)中也公开了常规的化学镀方法。
为了保证被镀材料的良好粘附性，优选在镀前对铝基片28进行彻底清洗，以除去如氧化物和油酯等的表面物质。优选的镍合金包括约9-12wt％的磷，更优选为约10-12wt％。
所述P-Ni镀层80足够厚，以使其附着在基片上，且又能使其在于该镍表面上形成如氧化铝、SiC、Si3N4、BC、AlN等陶瓷镀层之前被加工。该P-Ni镀层80可具有任何合适的厚度，如至少约0.002英寸、优选0.002-0.010英寸、更优选0.002-0.004英寸的厚度。
在于铝基片28上沉积P-Ni镀层80后，可以用任何适当的技术使该镀层喷砂或糙化，然后再镀陶瓷材料。该陶瓷材料优选被热喷镀到磷镍镀层80上。这样就为经糙化的层80与熔融的陶瓷颗粒间提供了特别好的结合。当陶瓷镀层冷却时，会给镀层80一个高的机械压力且使在镀层90中形成的裂纹减到最少。陶瓷镀层90可包括任何所需的陶瓷材料或材料的组合，如Al2O3、SiC、Si3N4、BC、AlN、TiO2等。
可以用如化学气相沉积或RF溅镀的任何沉积技术来镀涂陶瓷镀层。优选的镀涂方法是通过热喷镀，在热喷镀中陶瓷粉末被熔融且在气流的带动下结合到被喷镀的组件上。热喷镀技术的优点是金属体只有面对热喷枪的侧面被镀，而其它地方可以用遮蔽物保护起来。常用的热喷镀技术包括等离子体喷镀，其在Pawlowski的《热喷镀科学与工程》(The Science and Engineering of Thermal SprayCoating)(John Wiley，1995)中都有记载。
在优选的实施方案中，陶瓷层90是在P-Ni层80上等离子体喷镀氧化铝至合适的厚度而被沉积上的，该厚度如为约0.005-0.040英寸，优选为0.010-0.015英寸，选择该氧化铝层的厚度，以与反应器中将要遇到的等离子体环境(如蚀刻、CVD等)相容。该氧化铝层90可被镀涂在如上所述的整个或部分反应器腔室和组件上。优选将其镀涂在可能或不可能暴露于等离子体环境的区域上，如直接与等离子体接触的部分或位于腔室组件(如衬套等)后面的部分，以防止镍和/或铝污染在反应器腔室中加工的半导体基片。因此根据本发明的一个优点，通过抑制由于腐蚀产生的粉尘，可使沉积膜中的令人不满意的蚀刻或不希望的针孔得到减少。
以上参照具体实施方案对本发明进行了详细描述。显然对于熟悉此领域的人来说，在不脱离所附权利要求的范围内，可以进行各种变化和改进，或采用等效的结构。

Claims (11)

1.一种对半导体加工设备组件的金属表面进行镀涂的方法，该方法包括：
(a)在半导体加工设备组件的金属表面上沉积磷镍镀层；
(b)在所述磷镍镀层上沉积陶瓷镀层，其中所述陶瓷镀层构成最外层表面；
并且其中：
(i)所述组件是等离子体腔室侧壁，所述磷镍镀层被沉积在所述侧壁暴露的内表面上；
(ii)所述金属表面是经过阳极化处理或未经阳极化处理过的铝或铝合金；
(iii)所述陶瓷镀层包括Al2O3、SiC、Si3N4、BC或AlN；
并且所述镀涂方法进一步包括在沉积所述陶瓷镀层之前，对磷镍镀层进行表面糙化处理，所述陶瓷镀层是通过等离子体喷镀所述陶瓷镀层于所述磷镍镀层上而被沉积在糙化的磷镍镀层上，以便全部或部分覆盖所述磷镍镀层。
2.如权利要求1所述的镀涂方法，其中所述磷镍镀层是通过化学镀而被沉积上的。
3.如权利要求1所述的镀涂方法，其中所述磷镍镀层包括9-12wt％的磷。
4.如权利要求1所述的镀涂方法，其中所述磷镍镀层的厚度为0.002-0.004英寸。
5.如权利要求1所述的镀涂方法，其中所述陶瓷镀层的厚度为0.005-0.040英寸。
6.一种半导体加工设备的组件，其包括：
(a)金属表面；
(b)在所述金属表面上的磷镍镀层；和
(c)在所述磷镍镀层上的陶瓷镀层，其中所述陶瓷镀层构成最外层表面；
并且其中：
(i)所述组件为等离子体腔室侧壁；
(ii)所述金属表面是经过阳极化处理或未经阳极化处理过的铝或铝合金；
(iii)所述陶瓷镀层包括Al2O3、SiC、Si3N4、BC或AlN；所述磷镍镀层包括与陶瓷镀层接触的经糙化的表面，且该陶瓷镀层是热喷镀镀层。
7.如权利要求6所述的组件，其中所述磷镍镀层中含有9-12wt％的磷。
8.如权利要求6所述的组件，其中所述磷镍镀层的厚度为0.002-0.004英寸。
9.如权利要求6所述的组件，其中所述陶瓷镀层是等子体喷镀的氧化铝镀层，其厚度为0.005-0.030英寸。
10.如权利要求6所述的组件，其中所述陶瓷镀层是抗开裂的。
11.一种在包含组件的等离子体腔室中加工半导体基片的方法，该方法包括使半导体基片的暴露表面与等离子体接触；
其中所述组件包括：
(a)金属表面，该金属表面是经过阳极化处理或未经阳极化处理过的铝或铝合金；
(b)在所述金属表面上的磷镍镀层；和
(c)在所述磷镍镀层上的陶瓷镀层，其中所述陶瓷镀层构成最外层表面；
并且其中：
(i)所述组件为等离子体腔室侧壁；和
(ii)所述陶瓷镀层包括在磷镍镀层上的热喷镀的陶瓷镀层，并且该陶瓷镀层包括Al2O3、SiC、Si3N4、BC或AlN，以及所述磷镍镀层包括与陶瓷镀层接触的经糙化的表面。
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