CN1332267A - 使用连续淀积技术淀积难熔金属层的方法与装置 - Google Patents

使用连续淀积技术淀积难熔金属层的方法与装置 Download PDF

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CN1332267A
CN1332267A CN01121274A CN01121274A CN1332267A CN 1332267 A CN1332267 A CN 1332267A CN 01121274 A CN01121274 A CN 01121274A CN 01121274 A CN01121274 A CN 01121274A CN 1332267 A CN1332267 A CN 1332267A
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substrate
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席明
A·辛哈
M·克里
A·W·马克
潘容苏
雷春来
钟华
卢新良
赖康
K·A·立陶
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Applied Materials Inc
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Abstract

形成难熔金属层的方法和系统,其特征在于:通过连续淀积技术对衬底成核,在该连续淀积技术中,衬底依次暴露于第一和第二反应气体中,随之形成层,通过气相淀积,对成核层进行化合物的大块淀积,该化合物包含于第一和第二反应气体中。所有的处理步骤可以在相同或者不同的处理室内进行。例如,成核可以在不同于进行大块淀积的处理室的处理室内进行。还公开了用于控制所得到的层中的氟原子的存在的技术,该氟原子的存在在成核的过程中为所用载体气体的函数。

Description

使用连续淀积技术淀积难熔金属层的方法与装置
本发明涉及对于半导体衬底的处理。具体的说，本发明涉及在半导体衬底上淀积难熔金属层的改进方法。
半导体制造业不断要求在增加淀积于具有较大表面面积衬底上的各层的均匀性的同时可以获得较高的生产率。这些与材料相结合的相同因素也可以提供在单位面积衬底上的电路的较高集成度。随着电路集成度的增加，对较高均匀性及有关层厚的过程控制的要求就会增加。结果，已发展了多种具有成本效益的在衬底上淀积层的技术，该技术同时保持对层的特性的控制。化学气相淀积(CVD)是最普通的用于在衬底上淀积层的淀积方法之一。CVD是依赖流量的淀积技术，为产生所要得到的均匀厚度层，该技术需要精确控制衬底温度以及引入处理室的前体。由于会使处理室的设计以及为保持足够均匀性的气体流动技术变得更复杂，这种需要在衬底尺寸增加时变得更苛刻。
与CVD相比，可以进行较多步骤涂敷的CVD的派生技术为原子层淀积(ALD)。ALD基于最初用于制造电致发光显示器的原子层外延(ALE)。ALD用化学吸收作用以在衬底表面形成反应前体分子的饱和单层。它通过向淀积室里交替脉冲输入适当的反应前体而实现。每次反应前体的输入被不活泼气体冲洗隔开，以提供附加于先前淀积层的新原子层，从而在衬底上形成均匀层。重复该循环以形成所需厚度的层。ALD技术的缺点是淀积速度较低，小于典型CVD技术至少一个数量级。
以高淀积速度形成膜层和提供足够分步涂敷是相互冲突的特性，经常需要为获得一方而牺牲另一方。在形成将由介电层隔开的邻近金属层连接起来的接点的过程中，当难熔金属层淀积以涂敷间隙或者通路时这种冲突就尤其明显。在历史上，为了廉价快速形成接点，使用CVD技术以淀积诸如难熔金属的导电材料。由于半导体电路集成度的增加，在较多步骤涂敷中使用钨。结果，由于该方法大的产量，使用CVD技术淀积钨在半导体加工中获得广泛应用。
但是，用传统CVD方法淀积钨存在几个缺点。例如，在半导体衬底上钨层的涂敷层淀积在400℃是十分耗时的。钨的淀积速度可以通过增加淀积温度而提高，该淀积温度可以增加到诸如500～550℃。但是，在该较高范围下的温度会损害结构和正在形成的集成电路的下层部分的完整性。由于导致产生反射率低于硅基片20％的相对粗糙表面，使用钨还会妨碍在制作过程的光刻步骤。最后，已表明钨难于均匀淀积。已表明对于钨会带来大于1％的膜厚的变化，由此会妨碍对层的电阻系数的控制。已有几种针对克服上述缺点而进行的尝试。
例如，在受让于本发明受让人的Chang等人的美国专利号为5028565的专利及其它专利中，公开了通过改变淀积化学而提高钨的均匀性的方法。该方法包含在相关部分中在通过大块淀积进行淀积钨前在中间阻挡层上形成成核层。成核层从六氟化钨、氢、硅烷和氩气的气体混合物中形成。成核层被描述为提供促进均匀钨层在其上淀积的生长点的层。成核层的优点被描述为取决于所用阻挡层。例如阻碍层由氮化钛形成时，钨层厚度均匀性提高差不多15％。当阻挡层由溅射钨或者溅射钛钨形成时，成核层的优点不太明显。
因此，需要提供提高淀积于半导体衬底上的难熔金属层的特性的技术。
形成难熔金属层的方法和系统，其特征在于：通过连续淀积技术对衬底成核，在该连续淀积技术中，衬底依次暴露于第一和第二反应气体中，随之形成层，通过气相淀积，对成核层进行化合物的大块淀积，该化合物包含于第一和第二反应气体中之一。所有的处理步骤可以在相同或者不同的处理室内进行。例如，成核可以在不同于进行大块淀积的处理室的处理室内进行。还公开了用于控制所得到的层中的氟原子的存在的技术，该氟原子的存在为在成核的过程中所用载体气体的函数。
图1为根据本发明的半导体处理系统的透视图；
图2为上述图1中处理室的详细说明图；
图3为在连续淀积过程中第一分子在衬底上淀积的示意图；
图4为在连续淀积以形成难熔金属层的过程中第二分子在衬底上淀积的示意图；
图5为根据本发明，引入如上面图2中所示的处理室中的气体浓度，与存在于处理室中的气体的时间的图解图；
图6为根据本发明，ALD循环次数与层厚的关系的图解图，该层使用连续淀积技术形成于衬底上；
图7为根据本发明，连续淀积循环次数与层的电阻系数的关系的图解图，该层使用连续淀积技术形成于衬底上；
图8为根据本发明，层的淀积速度与衬底温度的关系的图解图，该层使用连续淀积技术形成于衬底上；
图9为根据本发明，层的电阻系数与衬底温度的关系的图解图，该层使用连续淀积技术形成于衬底上；
图10为根据本发明的布线衬底的剖面图，该布线衬底具有通过连续淀积技术形成于其上的成核层；
图11为根据本发明的如图10所示的衬底的局部剖面图，通过CVD在成核层上形成有难熔金属层；
图12为根据本发明的第一实施例，在图3中所示的气体的成分的图解图；
图13为根据本发明的第二实施例，在图5中所示的气体的成分的图解图；
图14为在Ar或N2为载体气体时氟的含量与难熔金属层的深度的关系的图解图，该难熔金属层使用ALD形成于衬底上；
图15为在H2为载体气体时氟的含量与难熔金属层的深度的关系的图解图，该难熔金属层使用ALD形成于衬底上。
如图1所示，例举性基片处理系统包含一个或者多个处理室12和14，该处理室置于由壁18围成的共同工作区域16中。处理室12和14与控制器22保持基线联系，该控制器与图中标为24和26的一个或者多个监视器相连。监视器一般显示与处理室12和14相关联的过程的信息。监视器之一26置于壁18上，而监视器24仍置于工作区域16中。处理室12和14的操作控制可以通过使用光笔而实现，以使之与控制器22相连，该光笔与监视器24和26之一相连。例如，光笔28与监视器24相连并通过监视器24促进与控制器22的联系。光笔39通过监视器26促进与控制器22的联系。
参照图1和2，每个处理室12和14包含：具有基壁32的外壳30，置于基壁32对面的盖子34，延伸于两者之间的侧壁36。外壳30界定了室37，基架38置于处理室37内，以支撑诸如半导体基片的衬底42。可以通过位移装置(未示出)将基架38上升至盖子34和基壁32之间，但是其位置为典型安装位置。处理气体供给装置39a、39b和39c通过喷嘴40与处理室37保持流体联通。出自供给装置39a、39b和39c中的气体的流动调节通过流动阀完成。
根据特定的处理，衬底42可以在层淀积前通过嵌入基架38的加热器被加热至所需的温度。例如，可以通过交流电源43供给加热元件44电流而对基架38进行电阻式加热。衬底42反过来被基架38加热，并可保持在诸如约20～750℃的所需处理温度范围内。诸如热电偶的温度传感器46也被嵌入基片支撑部件基架38中，以通过传统方式监控基架38的温度。例如，将所测温度用于反馈回路中，以控制由电源43施加于加热器44的电流，这样衬底温度就可保持或者控制在适于特定处理的所需温度。另外，也可以采用辐射加热装置(未示出)加热基架38。使用真空泵48抽空处理室37，以有助于保持适当的气体流动和处理室37中的压力。
参照图1和3，上述处理室12和14的其中之一或两者都可以通过连续淀积技术在衬底上淀积难熔金属层。根据本发明的连续淀积技术的一个例子包含原子层淀积(ALD)。根据处理的特定阶段，难熔金属层可以在制成衬底42的材料上淀积，该材料诸如SiO2。难熔金属层也可以在预先形成于衬底42上的层上淀积，该层诸如钛和氮化钛等。
在根据本发明的连续淀积技术中，此处为Aax的一炉第一处理气体导致产生在衬底42上淀积的A层，该衬底具有暴露于处理室37中的配位基表面。然后，清洗气体进入处理室37以冲洗去未被结合进入A层的气体Aax。在从处理室37中冲洗去Aax后，第二炉气体Bbx进入处理室37。衬底表面上配位基与b配位基和B原子反应，释放出诸如ab和aA的分子，该分子从衬底42中离开，然后被从处理室37中抽去。通过这种方式，包含层B的化合物的表面保留在衬底42上并暴露于处理室37中，如图4所示。B化合物层的成分可以为使用ALD形成的单层原子。另外，化合物B层可以包含多层原子。在这种情况下，第一处理气体可以包含处理气体的混合物，每一种处理气体具有可吸附于衬底42上的原子。该过程一个循环接着一个循环，直到得到所需的厚度。
参照图2和5，虽然可以使用各种类型的处理气体，在本实施例中，处理气体Aax包含B2H6，并且Bbx为WF6。使用两种清洗气体：Ar和N2。每一种处理气体与载体气体一起流入处理室37，在本实施例中为下列之一：WF6与Ar一起进入，B2H6与N2一起进入。但是，注意清洗气体可与下面着重详述的载体气体不同。根据本发明的ALD技术的一个循环包含清洗气体N2在时间t1内流入处理室37中，该时间t1在B2H6流入处理室37前，接近0.01～15秒。在0.01～15秒的时间t2内，处理气体B2H6与载体气体一起流入处理室37内，在本实施例中载体气体为N2。0.01～15秒之后，停止流入B2H6，并且在0.01～15秒的附加时间t3内继续保持N2的流入，以冲洗掉处理室中的B2H6。在时间t4内，尽可能多地抽空处理室37内的大部分气体。在抽空处理室37后，在0.01～15秒的时间t5引入载体气体Ar，在该时间t5后，在时间t6内将处理气体WF6与载体气体Ar一起引入处理室37内。时间t6持续0.01～15秒。处理气体WF6流入处理室37在其开始后的0.01～15秒后停止。在处理气体WF6停止流入处理室37后，在0.01～15秒的附加时间t7内继续保持Ar的流入。然后，在时间t8内尽可能抽空处理室内的气体。抽空过程如上持续近30秒，这样就构成了根据本发明的连续淀积技术的一个循环。
使用连续淀积技术的优点为多方面的，包含：层的形成与流量无关，这样就提供了与衬底尺寸无关的淀积的均匀性。例如，在同一室内在所测量的200mm和32mm衬底上淀积的层的均匀性和厚度的差异是微乎其微的。这是由于连续淀积技术的自我限制的特性而导致的。并且，该技术有利于在复杂外形上进行无余量分步涂敷。
除此之外，如图4所示，通过使用连续淀积技术可以在将其电阻减少到最小时很容易控制层B的厚度。如图6所示，从线50的斜率可以看出钨层厚度与所用形成钨层的循环次数成比例。但是，如图7中的曲线52的斜率所示，钨层的电阻系数相对与层厚无关，这样，使用连续淀积技术，可以很容易控制难熔金属层的厚度，该厚度作为处理气体引入处理室的循环次数的函数，而对电阻系数的影响微乎其微。
参照图4和8，可以发现对淀积速度的控制依赖于衬底42的温度。如线54的斜率所示，衬底42温度的上升会增加钨层B的淀积速度。例如，在56处可以看出，在250℃的温度下淀积速度接近2/循环。但点58处，在450℃的温度下淀积速度接近5/循环。但是，如图9中的曲线59的斜率所示，钨层的电阻系数实际上与层厚无关。结果，钨层的淀积速度可以作为温度的函数而被控制，而不会损坏电阻系数的均匀性。但是应减少淀积难熔金属的全部层的时间。
因此，淀积过程可包含难熔金属层的大块淀积(bulkdeposition)。难熔金属的大块淀积在普通的处理室里一般发生在成核层形成之后。具体的说，在本实施例中，钨层的成核在使用上述连续淀积技术的室12里发生，其衬底42被加热至200～400℃，处理室37被加压至1～10Torr。如图10所示，约12～20nm的成核层60形成于布线衬底42上。可以看出，衬底42包含阻挡层61和具有多个通路63的布线层。成核层在涂敷通路63的布线层的邻近形成。可以看出，使用ALD技术的成核层60可以提供100％的分步涂敷。为增加形成全部钨层的时间，钨在成核层上的大块淀积通过CVD技术实现，而衬底42置于相同的处理室12中，如图1所示。大块淀积可以通过众所周知的技术而实现。通过这种方式，就在具有纵横比约为6∶1的通路的布线层上得到了提供彻底的塞子填充的钨层65，如图11所示。
在另一实施例中，可以实施分为两部分的淀积过程，在该过程中，难熔金属层的成核在不同于在其中形成有难熔金属层的剩余部分的室的室中进行。具体的说，在本实施例中，钨层的成核通过上述的诸如ALD的连续淀积技术在室12中进行。最后，加热衬底42至200～400℃，加压处理室37至1～10Torr。如图10所示，约12～20nm的成核层60形成于布线衬底42上。可以看出，衬底42包含阻挡层61和具有多个通路63的布线层。成核层邻近于涂敷通路63的布线层形成。可以看出，使用ALD技术的成核层60可以提供100％的分步涂敷。
使用CVD技术，钨在成核层60上的大块淀积物在衬底42置于处理室14时形成，该处理室14如图1所示。大块淀积可以通过众所周知的技术实现。通过这种方式，就在具有纵横比约为6∶1的通路的布线层上得到了提供完全塞子填充的钨层65，如图11所示。实施上述分为两部分的淀积过程可以减少形成所需具有高性能的钨层的时间。
前已述及，在本发明另一实施例中的载体气体可以不同于清洗气体，如图12所示。在时间段t1、t3、t5和t7内引入的清洗气体包含Ar。在时间段t2和t6内引入的载体气体包含N2。这样，在时间段t2内，引入处理室的气体包含B2H6和H2的混合气，在时间段t6内，混合气包含WF6和N2。在时间段t4和t8内的冲洗过程同上述与图5相关的冲洗过程相同。在又一实施例中，如图13所示，在时间段t2和t6内的载体气体包含H2，而在时间段t1、t3、t5和t7内引入的清洗气体包含Ar。在时间段t4和t8内的冲洗过程如上所述。结果，在时间段t2内引入处理室37中的混合气包含B2H6和H2，在时间段t6内包含WF6和H2。
使用载体气体H2所带来的好处是可以提高钨层B的稳定性。具体的说，通过比较图14中的曲线66和图15中的曲线68，可以看出当使用H2作为载体气体时，与使用N2或Ar相比，图10中所示的成核层60中氟化物的浓度较低。
如图14和15所示，曲线66的顶点与最低点表明氟化物的浓度可达到超过每立方厘米1×1021原子，以及可低于每立方厘米1×1019原子。但是，曲线68表明氟化物浓度在顶点处明显低于每立方厘米1×1021原子，并且在最低点明显低于每立方厘米1×1017原子。这样，使用H2作为载体气体提供了更加稳定的膜，即降低了氟化物扩散进入衬底或者邻近层的可能性。同时，这样通过避免形成可以导致增加氟化物浓度的金属氟化物，从而降低了难熔金属层的电阻。这样，成核层的稳定性及其电阻系数可以作为所用载体气体的函数而得到控制。当使用ALD技术，即不使用其它的诸如CVD的淀积技术，完全淀积难熔金属层时也会出现同样的效果。
再参照图2，可以使用由控制器22执行的计算机程序对淀积钨层的过程进行控制。最后，控制器22包含中央处理器(CPU)70、诸如随机存取存储器(RAM)72的非永久性存储器和诸如软盘驱动器和硬盘驱动器的永久存贮介质，该软盘驱动器用于使用软盘。计算机程序指令可以用各种传统计算机可读程序语言编写；例如68000汇编语言、C、C++、Pascal和Fortran等。通过传统的文本编辑器将适当的程序指令输入一个文件，或者多个文件，并且保存或者录入诸如硬盘74的计算机可读介质中。如果输入的指令文本为高级语言，指令被编译，然后将生成的编译指令与预编译程序Windows库存程序相连接。为执行连接并编译目标指令，系统用户调用目标指令，使CPU70将指令装入RAM72中。然后CPU70读取并执行指令以实现程序规定的任务。
虽然本发明已对特定实施例作出说明，熟知本领域的可以认识到，反应条件的各种变化，即温度、压力和膜厚等，可以被替换并包含于其中。另外，当分成两部分的淀积过程已经被描述为在相同的系统内进行时，大块淀积可以发生于主机架淀积系统的处理室内，该主机架淀积系统不同于处理室用作淀积成核层的主机架淀积系统。最后，除了钨外，还可以淀积其它的难熔金属，并且，可以使用其它淀积技术以取代CVD。例如物理气相淀积(PVD)技术或者使用CVD和PVD技术的组合。本发明的范围不应限于上面所述。本发明的范围更适于基于这里所述的权利要求书，该权利要求书包含其等同物的全部范围。

Claims (14)

1.一种在置于处理室内的衬底上形成层的方法，该方法包含：
通过依次将所述衬底暴露于第一和第二反应气体中以形成成核层；
通过气相淀积对所述成核层进行化合物的大块淀积，在所述成核层上形成大块淀积物层，该化合物包含于所述第一和第二反应气体其中之一。
2.如权利要求1所述的方法，其中，形成所述成核层和形成所述大块淀积物层在同一个处理室内进行。
3.如权利要求1所述的方法，进一步包含：提供第一和第二处理室，在形成所述成核层前将所述衬底置于所述第一处理室内，在形成所述大块淀积物层前将所述衬底置于所述第二处理室里，其中，形成所述成核层发生于所述第一处理室内并且形成所述大块淀积物层发生于所述第二处理室内。
4.如权利要求1所述的方法，其中，第二反应气体具有与其相关的氟原子，第一和第二反应气体各自与载体气体一起被引入所述处理室内，并且进一步包含控制所述成核层中氟原子的量，该氟原子的量为所述载体气体的函数。
5.如权利要求1所述的方法，其中，在所述成核层上形成大块淀积物层包含使用化学气相淀积形成所述大块淀积物层。
6.如权利要求1所述的方法，其中，在所述成核层上形成大块淀积物层包含使用物理气相淀积形成所述大块淀积物层。
7.如权利要求1所述的方法，其中，形成成核层进一步包含将所述第一和第二气体引入其中，以在将所述衬底暴露于所述第二反应气体前，通过在其中引入清洗气体清空所述处理室中的所述第一反应气体。
8.如权利要求1所述的方法，其中，形成成核层进一步包含，在引入所述第二反应气体前，通过抽空所述处理室中的所有气体清空所述处理室中的所述第一反应气体。
9.如权利要求1所述的方法，其中，形成成核层进一步包含，在将所述衬底暴露于所述第二反应气体前，通过引入清洗气体继而抽空所述处理室里的所有气体，清空所述处理室中的所述第一反应气体。
10.如权利要求1所述的方法，其中，形成成核层包括形成包含含有氢的化合物和难熔金属的交替叠层。
11.一种对于衬底的处理系统，所述系统包含：
限定处理室的装置；
支撑部件，该支撑部件置于所述处理室里，用以支撑所述衬底；
与所述处理室保持流体联系的气体传输系统；
与所述处理室保持热联系的温度控制系统；
与所述处理室保持流体联系的压力控制系统；
与所述气体传输系统、所述温度控制系统和所述压力控制系统保持电子联系的控制器；
与所述控制器保持数据联系的存贮器，所述存贮器包含其中录入有计算机可读程序的计算机可读介质，所述计算机可读程序包含第一批指令，该指令用以控制所述气体传输系统，以通过依次将所述衬底暴露于第一和第二反应气体中而形成成核层；以及第二批指令，该指令用以控制所述气体传输系统，以通过对所述成核层进行化合物的气相淀积，在所述成核层上形成大块淀积物层，该化合物包含于所述第一和第二反应气体中之一。
12.如权利要求11所述的处理系统，进一步包含：界定附加处理室的附加装置；附加支撑部件，该附加支撑部件置于所述第二处理室里以支撑所述衬底；与所述第二处理室保持热联系的附加温度控制系统；与所述第二处理室保持流体联系的附加压力控制系统；置于所述第一处理室和所述附加处理室之间的自动操作装置，所述气体传输系统与所述附加处理室保持流体联系，并且所述控制器与所述附加温度控制系统、所述压力控制系统和所述自动操作装置保持电子联系；所述第一批指令进一步包含第一子程序，该第一子程序用以控制所述气体传输系统，以在所述衬底在所述处理室内时形成所述成核层，且所述第二批指令包含第二子程序，该第二子程序用以控制所述自动操作装置，以在所述处理室和所述附加处理室之间移动衬底，并且控制所述气体传输系统，以在所述衬底置于所述第二处理室里时形成所述大块淀积物层。
13.如权利要求12所述的处理系统，其中，所述第二反应气体具有与其相关连的氟原子，并且所述第一批指令进一步包含将所述第一和第二反应气体各自与载体气体一起引入所述处理室内的子程序，并且所述计算机可读程序进一步包含第三批指令，该第三批指令用以控制与成核层相关连的所述氟原子的量，该氟原子的量为所述载体气体的函数。
14.如权利要求13所述的处理系统，其中，所述计算机可读程序包含附加指令，通过将清洗气体引入其中，以在将所述第二反应气体引入之前清空所述处理室内的所述第一反应气体。
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