CN112154532A - 提供等离子体原子层沉积的方法 - Google Patents

提供等离子体原子层沉积的方法 Download PDF

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CN112154532A
CN112154532A CN201980031266.3A CN201980031266A CN112154532A CN 112154532 A CN112154532 A CN 112154532A CN 201980031266 A CN201980031266 A CN 201980031266A CN 112154532 A CN112154532 A CN 112154532A
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power
plasma
layers
ald
ald layers
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普尔凯特·阿加瓦尔
普鲁肖塔姆·库马尔
阿德里安·拉沃伊
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Lam Research Corp
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Abstract

提供了一种用于在衬底上沉积层的方法。在衬底上方沉积多个等离子体原子层沉积(ALD)层，其中以第一RF功率沉积多个ALD层中的每个等离子体ALD层。所述多个等离子体ALD层被致密化，其包括使用大于第一RF功率的第二RF功率来产生致密化等离子体，其中多个等离子体ALD层中的至少一个被致密化。

Description

提供等离子体原子层沉积的方法
相关申请的交叉引用
本申请要求于2018年5月8日提交的美国申请No.15/974,500的优先权，其通过引用并入本文以用于所有目的。
背景技术
本公开涉及半导体器件的形成。更具体地，本公开涉及半导体器件的形成，其中，通过等离子体原子层沉积沉积层。等离子体原子层沉积提供了多个循环，其中每个循环都沉积薄层。
发明内容
为了实现前述目的并且根据本公开的目的，提供了一种用于在衬底上沉积层的方法。在衬底上方沉积多个等离子体原子层沉积(ALD)层，其中以第一RF功率沉积多个ALD层中的每个等离子体ALD层。所述多个等离子体ALD层被致密化，其包括使用大于第一RF功率的第二RF功率来产生致密化等离子体，其中多个等离子体ALD层中的至少一个被致密化。
本公开的这些特征和其它特征将在下面在本公开内容的详细描述中并结合以下附图进行更详细的描述。
附图说明
在附图中以示例而非限制的方式示出了本公开，并且附图中类似的附图标记表示相似的元件，其中：
图1是一实施方案的高级流程图。
图2是可以在一实施方案中使用的处理室的示意图。
图3是可以用于实施一实施方案的计算机系统的示意图。
图4是根据一实施方案处理的堆叠件的示意性截面图。
图5A-C是根据一实施方案处理的另一堆叠件的示意性截面图。
图6是ALD工艺的更详细的流程图。
图7是致密化工艺的更详细的流程图。
图8是另一ALD工艺的更详细的流程图。
图9是规则的ALD、10个循环的软ALD、20个循环的软ALD以及30个循环的ALD与以埃为单位的氧化硅厚度的关系的柱状图。
具体实施方式
现在将参考附图中所示的几个优选实施方案来详细描述本公开。在下面的描述中，阐述了许多具体细节以便提供对本公开的彻底理解。然而，对于本领域技术人员显而易见的是，本公开可以在没有这些具体细节中的一些或全部的情况下实施。在其他情况下，未详细描述公知的工艺步骤和/或结构，以免不必要地使本公开不清楚。
氧化物(二氧化硅(SiO2))膜的质量在某些应用中非常重要，因为它直接影响器件的性能和良率。特别是随着器件尺寸的缩小，具有高密度/高质量的亚纳米氧化膜的开发变得非常重要。在常规工艺中，通过高RF功率转换等离子体可获得良好的质量。但是，高射频(RF)功率转换等离子体很容易损坏下伏的衬底，从而导致不良的器件性能和良率。
为了便于理解，图1是一实施方案的高级流程图。确定在常规RF功率下的等离子体ALD沉积的等离子体穿透深度(步骤104)。以比常规RF功率低的第一RF功率来沉积多个等离子体ALD层(步骤108)。通过使用大于第一RF功率的第二RF功率产生致密化等离子体来使多个ALD层致密化，其中，对多个ALD层中的全部进行致密化(步骤112)。以高于第一RF功率的第三RF功率沉积多个等离子体ALD层(步骤116)。
实施例
图2是可以在一个实施方案中使用的处理室的示意图。在一个或多个实施方案中，处理室200包括在由室壁252包围的室249内的提供气体入口的气体分配板206和静电卡盘(ESC)208。在室249内，将晶片203定位在ESC 208上方，ESC 208是衬底支撑件。边缘环209围绕ESC208。ESC源248可向ESC 208提供偏置。气体源210通过气体分配板206连接至室249。ESC温度控制器250连接至ESC 208。射频(RF)源230向下电极和/或上电极提供RF功率，下电极和/或上电极在该实施方案中为ESC 208和气体分配板206。在示例性实施方案中，400kHz(千赫兹)电源、60MHz(兆赫兹)电源以及可选的2MHz电源、27MHz电源构成RF源230和ESC源248。在该实施方案中，上电极接地。在该实施方案中，针对每种频率提供一个发生器。在其他实施方案中，发生器可以在单独的RF源中，或者单独的RF发生器可以连接到不同的电极。例如，上电极可以具有连接到不同RF源的内电极和外电极。在其他实施方案中可以使用RF源和电极的其它布置。控制器235可控地连接到RF源230、ESC源248、排放泵220和气体源210。这种室的一个示例是由Lam Research Corporation(Fremont，CA)制造的StrikerTMOxide系统。
图3是示出适用于实现在实施方案中使用的控制器235的计算机系统300的高级框图。计算机系统可以具有从集成电路、印刷电路板和小型手持设备到超大型计算机的许多物理形式。计算机系统300包括一个或多个处理器302，并且还可以包括电子显示设备304(用于显示图形、文本和其他数据)、主存储器306(例如随机存取存储器(RAM))、存储设备308(例如，硬盘驱动器)、可移动存储设备310(例如，光盘驱动器)、用户界面设备312(例如，键盘、触摸屏、小键盘、鼠标或其他指点设备等)和通信接口314(例如，无线网络接口)。通信接口314允许通过链路在计算机系统300和外部设备之间传送软件和数据。系统还可以包括与上述设备/模块连接的通信基础设施316(例如，通信总线、交叉连接杆或网络)。
经由通信接口314传送的信息可以是例如电子信号、电磁信号、光学信号之类的信号形式或能够经由通信链路由通信接口314接收的其它信号，通信链路携带信号并可以使用导线或电缆、光纤、电话线、蜂窝电话链路、射频链路和/或其他通信信道实现。利用这样的通信接口，可以预期一个或多个处理器302可以在执行上述方法步骤的过程中从网络接收信息，或者可以向网络输出信息。此外，方法实施方案可以仅在处理器上执行，或者可以通过诸如因特网之类的网络与共享处理的一部分的远程处理器一起执行。
术语“非瞬态计算机可读介质”通常用于指代介质，诸如主存储器、辅助存储器、可移动存储设备、和存储设备，诸如硬盘、闪存存储器、磁盘驱动存储器、CD-ROM以及其他形式的持久性存储器，并且不应当被解释为涵盖瞬态标的物，如载波或信号。计算机代码的示例包括机器代码(诸如由编译器产生的)和含有由计算机使用解释器执行的较高级代码的文档。计算机可读介质也可以是由包含在载波中的计算机数据信号发送的并且代表能由处理器执行的指令序列的计算机代码。
在实施方案的实现方式的示例中，确定在常规RF功率下的等离子体ALD沉积的等离子体穿透深度(步骤104)。图4是堆叠件400的一部分的截面图，其中晶片404设置在中间层408下方，该中间层408设置在通过等离子体ALD沉积的多个高质量氧化硅层412下方。在等离子体ALD沉积期间，形成含氧等离子体，以将含硅前体转化为氧化硅。提供RF功率以提供含氧等离子体。RF功率被优化为使得多个氧化硅层412具有高质量。发现含氧的等离子体对中间层408造成损坏。在该示例中，测得的损坏厚度为约20埃(
Figure BDA0002767729120000041
)。用于确定穿透深度的工艺的示例将在详细描述其余工艺之后描述，因为用于确定穿透深度的工艺取决于用于以低于常规RF功率的第一RF功率沉积ALD层的方法。
将具有中间层的新衬底放置在等离子体处理室中。图5A是堆叠件500的一部分的截面图，其中晶片504设置在中间层508下方。在该示例中，中间层508是氮化硅。在其他实施方案中，中间层508可以是另一种材料，例如多晶硅、氧氮化硅(SiON)、碳硬掩模、光致抗蚀剂或含金属的层，含金属的层例如锗-锑-碲(GST)层。
以比常规RF功率低的第一RF功率沉积多个等离子体ALD层(步骤108)，从而产生软ALD氧化硅层。图6是为多个等离子体ALD层提供第一RF功率的更详细的流程图(步骤108)。形成前体层(步骤604)。在该示例中，为了沉积氧化硅，提供了硅烷的含硅前体，例如双(二乙基氨基)硅烷(BDEAS)、双(叔丁基氨基)硅烷(BTBAS)、二异丙基氨基硅烷(DIPAS)、三(二甲基氨基)硅烷(TDMAS)或其他硅烷。在该示例中，硅烷在中间层508的表面上形成单层。在该示例中，停止了含硅前体向等离子体处理室中的流动，并且通过使含氧气体流入等离子体处理室中(步骤608)来提供转化气体。在该示例中，转化气体包括氧化剂和惰性气体(inters)中的至少一种，例如氧化亚氮(N2O)、氦气(He)、氧气(O2)和氩气(Ar)中的至少一种。将转化气体被转化成等离子体(步骤612)。在此示例中，较低的RF功率用于将转化气体转化为等离子体。在该示例中，所提供的RF功率在500到1000瓦的范围内，其通过气体分配板206施加。也可以通过ESC 208施加在500瓦到1000瓦的范围内的偏置RF功率。来自转化气体的等离子体与含硅前体反应，以将含硅前体转化为氧化硅层。在0.1至1秒之间之后，停止转化气体的流动(步骤616)。重复该循环(步骤620)，直到沉积出厚度为约20埃的氧化硅沉积物为止，因为已确定损伤的厚度为约20埃，因此通过致密化在所提供的功率下的等离子体穿透了约20埃。
图5B是在已经沉积了多个等离子体ALD层512之后的堆叠件的一部分的截面图。因为该沉积工艺的RF功率比用于沉积高质量的氧化硅层的RF功率低，所以不会损坏中间层。优化RF功率，以最大程度地减少对中间层的损坏。结果，由于RF功率被优化以最小化损坏而不是被优化以提供最高质量的氧化硅沉积，因此沉积的氧化硅的质量较低(即较低的密度)。这样的较低质量的氧化硅沉积会降低由这种氧化硅沉积所制造的半导体器件的性能。
通过使用大于第一RF功率的第二RF功率产生致密化等离子体来致密化多个ALD层，其中，对多个ALD层中的全部进行致密化(步骤112)。图7是致密化多个ALD层的步骤(步骤112)的更详细的流程图。使致密化气体流入处理室(步骤704)。在该示例中，致密化气体包括H2、N2、Ar、N2O、O2和He中的一种或多种。使致密化气体转化成等离子体(步骤708)。在该示例中，被提供的第二RF是在通过气体分配板206施加的2500到5500瓦的范围内。也可以通过ESC 208施加2500到5500瓦的范围内的偏置RF功率。在0.1到1秒钟之后，停止致密气体的流动(步骤712)。在该示例中，用于致密化的RF功率大约等于用于提供优化的氧化硅沉积的RF功率。这种优化的氧化硅沉积提供了激励等离子体以到达所有多个层的RF功率，从而致密化所有多个层而不会损坏中间层508。致密化将ALD层转变为高质量的ALD层512，而不会损坏中间层508。
以高于第一RF功率的第三RF功率沉积多个等离子体ALD层(步骤116)，以沉积规则的ALD氧化硅层。图8是为多个等离子体ALD层提供高于第一RF功率的第三RF功率(步骤116)的更详细的流程图。在该示例中，为了沉积氧化硅，提供了硅烷的含硅前体，例如双(二乙基氨基)硅烷(BDEAS)、双(叔丁基氨基)硅烷(BTBAS)、二异丙基氨基硅烷(DIPAS)、三(二甲基氨基)硅烷(TDMAS)或其他硅烷(步骤804)。在该示例中，硅烷在先前沉积的ALD层的表面上形成单层。在该示例中，停止了含硅前体向等离子体处理室中的流动，并且通过使转化气体流入等离子体处理室(步骤808)中来提供转化气体。在该示例中，转化气体包括N2O、He、O2和Ar。将转化气体转化成等离子体(步骤812)。在该示例中，第三RF功率被用于将转化气体转化成等离子体。在该示例中，被提供的第三RF功率是在通过气体分配板206施加的2500到5500瓦的范围内。也可以通过ESC 208施加2500到5500瓦的范围内的偏置RF功率。来自转化气体的等离子体与含硅前体层反应，以将前体层转化为氧化硅。停止转化气体的流动(步骤816)。重复该循环(步骤820)，直到氧化硅沉积达到期望的厚度为止。图5C是在已经使用第三RF功率沉积了多个等离子体ALD层516之后的堆叠件的一部分的截面图。因为该沉积工艺具有高于第一RF功率的第三RF功率，所以高质量的氧化硅层被沉积。由于以第三RF功率沉积的ALD层516沉积在以第一RF功率沉积的ALD层512上方，因此以第一RF功率沉积的ALD层512会防止损坏中间层508。
如果致密化RF太低，则某些ALD层将不会被致密化，导致低质量的ALD层，从而可能增加器件缺陷。如果致密化RF太高，则中间层将被损坏，这可能会增加器件缺陷。为了提供高质量的氧化硅沉积，将致密化RF设置在所需的水平。因此，在提供致密化之前，必须将使用第一RF功率的ALD层沉积到一定厚度。如果厚度太小，则中间层508将被损坏。如果厚度太大，那么并不是所有的层都会致密化。结果，实施方案测量通过使用第二RF功率的等离子体引起的穿透深度，然后使用第一RF功率提供厚度等于该穿透深度的多个ALD层。
在一实施方案中，深度穿透的确定包括一系列厚度和泄漏研究。首先，以高于第一RF功率的第三RF功率将ALD膜沉积在裸Si衬底上，并进行泄漏和厚度的测量。然后，以低于常规RF功率的第一RF功率沉积ALD膜5、10、20和30个循环，然后使ALD膜致密化，然后进行厚度和泄漏测量。如果等离子体穿透大于软层，则由于在衬底处形成氧化硅，因此与期望的等离子体穿透深度相比，厚度将更高。如果等离子体穿透不足，则一些软层在致密化处理期间将不会致密化，并且与期望的等离子体穿透深度相比，所得的厚度将更高并且泄漏将更大。因此，如果我们绘制厚度与软ALD循环数的关系曲线，则等离子体穿透深度将达到最小值。图9是规则的ALD、10个循环的软ALD、20个循环的软ALD以及30个循环的软ALD与以埃为单位的氧化硅厚度的关系的柱状图。在该示例中，规则的ALD氧化硅沉积提供最厚的氧化硅层。软ALD氧化硅沉积的10个循环沉积最薄的氧化硅层。软ALD氧化硅沉积的20个循环会沉积下一个最薄的氧化硅层。软ALD氧化硅沉积的30个循环沉积下一个最薄的氧化硅层。从该图可确定，等离子体穿透为约10层的软ALD氧化硅沉积，因为随着附加循环导致的氧化硅厚度的增加归因于由于等离子体穿透不足而未被致密化工艺所致密化的软ALD氧化硅沉积层。
在一些实施方案中，在致密化期间提供的第二RF功率至少是为沉积较低功率等离子体ALD层而提供的第一RF功率的三倍。更优选地，在致密化期间提供的第二RF功率是为沉积较低功率的等离子体ALD层而提供的第一RF功率的至少五倍。在一些实施方案中，第三RF功率是第一RF功率的至少三倍。更优选地，第三RF功率是第一RF功率的至少五倍。在多种实施方案中，第一RF功率介于约500到1000瓦之间。在多种实施方案中，第二RF功率和第三RF功率比第一RF功率大500瓦以上。
在多种实施方案中，在中间层具有显著损坏之前，中间层具有阈值RF预算。RF暴露将通过RF功率乘以中间层暴露于RF功率的时间来计量。通过提供低RF功率以形成以第一RF功率沉积的多个等离子体ALD层，中间层具有低于阈值RF预算的RF暴露。尽管致密化使用较高的RF功率，但是由于通过多个等离子体ALD层防止了在致密化期间产生的等离子体到达中间层，因此致密化不会导致RF暴露超过RF预算。因而，致密化可以以比在第一RF下形成ALD层期间使用的RF功率大五倍的RF功率来执行，并且致密化还可以提供更长时间的RF。在一些实施方案中，在提供第一RF功率以形成多个等离子体ALD层期间的RF暴露被优化为大约等于RF预算。
在多种实施方案中，湿蚀刻速率比可用于指示是否使用较低的RF形成了多个ALD层，从而导致了较低质量和较低密度沉积，或者是否使用较高的RF形成了多个ALD层，从而导致高质量和较高的沉积。高质量的ALD层沉积的湿法蚀刻速率小于5。较低质量的ALD沉积法具有较高的湿法蚀刻速率。然而，在致密化之后，致密化的ALD致密化的湿蚀刻速率小于5。
在多种实施方案中，致密化气体可以是包括诸如氦气(He)或氩气(Ar)之类的惰性气体的气体。在一实施方案中，致密化气体可以基本上由氧气(O2)和He组成。在另一实施方案中，致密化气体可以基本上由O2和Ar组成。在其他实施方案中，致密化气体可以基本上由O2、He和Ar组成。
认为损伤在沉积膜的界面层处有任何变化。损伤可能是下层的氧化、下层的溅射或下层的化学蚀刻。
虽然已经根据几个优选实施方案描述了本公开，但是存在落在本公开的范围内的改变、修改、置换和各种替代等同方案。还应当注意，存在实现本公开的方法和装置的许多替代方式。因此，以下所附权利要求旨在被解释为包括落在本公开的真实精神和范围内的所有这样的改变、修改、置换和各种替代等同方案。

Claims (19)

1.一种在衬底上沉积层的方法，其包括：
在所述衬底上沉积多个等离子体原子层沉积(ALD)层，其中，以第一RF功率沉积所述多个ALD层中的每个等离子体ALD层；以及
使所述多个等离子体ALD层致密化，其包括使用大于所述第一RF功率的第二RF功率产生致密化等离子体，其中使所述多个等离子体ALD层中的至少一个致密化。
2.根据权利要求1所述的方法，其中，使所述多个等离子体ALD层致密化使所述多个等离子体ALD层中的全部致密化。
3.根据权利要求2所述的方法，其中在所述衬底上沉积所述多个等离子体ALD层使至少五个等离子体ALD层沉积。
4.根据权利要求2所述的方法，其中在所述衬底上沉积所述多个等离子体ALD层使至少十个等离子体ALD层沉积。
5.根据权利要求4所述的方法，其中来自所述致密化等离子体的离子不到达所述衬底。
6.根据权利要求2所述的方法，其中来自所述致密化等离子体的离子不到达所述衬底。
7.根据权利要求2所述的方法，其还包括：使用大于所述第一RF功率的第三RF功率在致密化的所述多个等离子体ALD层之上提供多个等离子体ALD层。
8.根据权利要求7所述的方法，其中，所述使用大于所述第一RF功率的第三RF功率在致密化的所述多个等离子体ALD层上提供多个等离子体ALD层包括：
使前体流动以形成前体层；
停止所述前体的流动；
提供转化气体；
以所述第三RF功率提供RF功率以使所述转化气体形成等离子体，该等离子体将所述前体层转化；以及
停止所述转化气体的流动。
9.根据权利要求2所述的方法，其中，所述第一RF功率在约500到1000瓦之间。
10.根据权利要求2所述的方法，其中，沉积所述多个ALD层使所述多个ALD层沉积至约10至
Figure FDA0002767729110000021
厚的厚度。
11.根据权利要求2所述的方法，其中，在所述衬底上沉积所述多个等离子体ALD层使多个氧化硅层沉积。
12.根据权利要求2所述的方法，其中，在所述衬底上沉积所述多个等离子体ALD层包括多个循环，其中每个循环包括：
使前体流动以形成前体层；
停止所述前体的流动；
提供转化气体；
以所述第一RF功率提供RF功率以使所述转化气体形成等离子体，该等离子体使所述前体层转化；以及
停止所述转化气体的流动。
13.根据权利要求12所述的方法，其中，所述多个循环被重复至少五次。
14.根据权利要求12所述的方法，其中，所述前体气体是含硅烷的气体。
15.根据权利要求2所述的方法，其中，所述第二RF功率是所述第一RF功率的至少五倍。
16.根据权利要求2所述的方法，其还包括确定在所述第二RF功率下的等离子体穿透深度。
17.根据权利要求16所述的方法，其中，所述转化气体包括N2O、He、O2或Ar中的至少一种。
18.根据权利要求2所述的方法，其中，所述使所述多个等离子体ALD层致密化包括：
提供致密化气体；以及
通过以所述第二RF功率提供RF功率，由所述致密化气体形成等离子体。
19.根据权利要求18所述的方法，其中，所述致密化气体包括H2、N2、Ar、N2O、O2或He中的至少一种。
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