CN112714945A - 半导体装置的制造方法 - Google Patents

半导体装置的制造方法 Download PDF

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CN112714945A
CN112714945A CN201980061504.5A CN201980061504A CN112714945A CN 112714945 A CN112714945 A CN 112714945A CN 201980061504 A CN201980061504 A CN 201980061504A CN 112714945 A CN112714945 A CN 112714945A
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electrode film
metal oxide
capacitor insulator
semiconductor device
annealing
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河野有美子
中村源志
P·戈贝尔
中林肇
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Tokyo Electron Ltd
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Abstract

本发明的半导体装置的制造方法包括第1层叠工序、第2层叠工序、第3层叠工序、第1退火工序和第4层叠工序。在第1层叠工序中，在基材上层叠第1电极膜。在第2层叠工序中，在第1电极膜上层叠电容绝缘物。在第3层叠工序中，在电容绝缘物上层叠金属氧化物。在第1退火工序中，对层叠于基材上的第1电极膜、电容绝缘物和金属氧化物进行退火。在第4层叠工序中，在进行了退火的金属氧化物上层叠第2电极膜。此外，电容绝缘物是包含锆和铪中的至少任一者的氧化物，金属氧化物是含有钨、钼和钒中的至少任一金属的氧化物。

Description

半导体装置的制造方法
技术领域
本发明的各种方面和实施方式涉及半导体装置的制造方法。
背景技术
下述的专利文献1～7中，记载有包含电容器的半导体装置的制造方法。
现有技术文献
专利文献
专利文献1：日本特开2014-229680号公报
专利文献2：日本特开2014-044993号公报
专利文献3：日本特开2013-058559号公报
专利文献4：日本特开2012-248813号公报
专利文献5：日本特开2012-064631号公报
专利文献6：国际公开第2010/082605号
专利文献7：日本特开平05-267567号公报
发明内容
发明要解决的技术问题
本发明提供一种能够抑制金属氧化物上的电极膜的膨胀和脱落的半导体装置的制造方法。
用于解决技术问题的技术方案
本发明的一个方面为半导体装置的制造方法，其包括第1层叠工序、第2层叠工序、第3层叠工序、第1退火工序和第4层叠工序。在第1层叠工序中，在基材上层叠第1电极膜。在第2层叠工序中，在第1电极膜上层叠电容绝缘物。在第3层叠工序中，在电容绝缘物上层叠金属氧化物。在第1退火工序中，对层叠于基材上的第1电极膜、电容绝缘物和金属氧化物进行退火。在第4层叠工序中，在进行了退火的金属氧化物上层叠第2电极膜。此外，电容绝缘物是包含锆和铪中的至少任一者的氧化物，金属氧化物是含有钨、钼和钒中的至少任一金属的氧化物。
发明效果
依照本发明的各种方面和实施方式，能够抑制金属氧化物上的电极膜的膨胀和脱落。
附图说明
图1是表示本发明的一实施方式中的半导体装置的制造方法的一例的流程图。
图2是表示半导体装置的制造过程的一例的图。
图3是表示半导体装置的制造过程的一例的图。
图4是表示半导体装置的制造过程的一例的图。
图5是表示半导体装置的制造过程的一例的图。
图6是表示研究了第2电极膜是否存在膨胀的实验结果的一例的图。
具体实施方式
下面，基于附图，对公开的半导体装置的制造方法的实施方式详细地进行说明。此外，公开的半导体装置的制造方法不由以下的实施方式限定。
作为DRAM(Dynamic Random Access Memory：动态随机存取存储器)的电容器等的半导体装置的构造，已知有电容绝缘物被2个金属电极膜夹着的MIM(Metal-Insulator-Metal：金属-绝缘体-金属)构造。这样的构造的半导体装置，在第1金属电极膜之上层叠氧化锆(ZrO2)等的电容绝缘物，在电容绝缘物之上层叠第2金属电极膜。而且，为了提高电容绝缘物的结晶性，对被第1金属电极膜和第2金属电极膜夹着的电容绝缘物进行退火(anneal)处理。
但是，为了在电容绝缘物的边界面形成偶极子而提高势垒高度(barrierheight)，有时在电容绝缘物之上层叠金属氧化物。当制造在电容绝缘物之上层叠有金属氧化物的构造的电容器时，在第1金属电极膜之上层叠了电容绝缘物、金属氧化物和第2金属电极膜后，进行退火处理以提高电容绝缘物的结晶性。
但是，在金属氧化物上层叠了第2金属电极膜后进行退火处理时，有时在金属氧化物与第2金属电极膜之间局部的产生空隙，第2金属电极膜膨胀。当在金属氧化物与第2金属电极膜之间局部地产生空隙时，金属氧化物与第2金属电极膜之间的接触变得不充分。此外，当在金属氧化物与第2金属电极膜之间产生空隙时，金属氧化物与第2金属电极膜之间的紧贴性降低，第2金属电极膜容易从金属氧化物脱落。
因此，本发明提供一种能够抑制金属氧化物上的电极膜的膨胀和脱落的技术。
[半导体装置的制造方法]
图1是表示本发明的一实施方式中的半导体装置的制造方法的一例的流程图。此外，图2～图5是表示各步骤中的被处理体W的状态的一例的截面图。通过本流程图所示的方法制造的被处理体W，用于半导体装置的制造。
首先，将硅等基材100送入第1成膜装置内，在基材100上层叠第1电极膜101(S10)。步骤S10是第1层叠工序的一例。在本实施方式中，第1电极膜101例如为氮化钛(TiN)。在步骤S10中，第1电极膜101例如通过使用钛的靶材在氮气气氛下进行的PVD(Physical VaporDeposition：物理气相沉积)，而在基材100上成膜。由此，例如如图2所示，在基材100上形成层叠有第1电极膜101的被处理体W。然后，将被处理体W从第1成膜装置送出。
接着，将被处理体W送入第2成膜装置内，在第1电极膜101上层叠电容绝缘物102(S11)。步骤S11是第2层叠工序的一例。在本实施方式中，电容绝缘物102例如为氧化锆。此外，作为其他方式，电容绝缘物102可以为氧化铪(HfO2)，也可以为包含锆(Zr)和铪(Hf)的氧化物。
在步骤S11中，电容绝缘物102例如通过反复进行吸附工序、第1吹扫工序、反应工序、第2吹扫工序的ALD(Atomic Layer Deposition：原子层沉积)，而在第1电极膜101上成膜。由此，例如如图3所示，在基材100上形成层叠有第1电极膜101和电容绝缘物102的被处理体W。
在步骤S11中的ALD中，被处理体W的温度例如为250℃，第2成膜装置内的压力例如为1Torr。此外，各工序的主要条件的一例，如下所示。
[吸附工序]
原料：TEMAZ(四乙基甲基氨基锆)
处理时间：5秒
[第1吹扫工序]
吹扫气体：氩气
流量：500sccm
处理时间：10秒
[反应工序]
反应气体：氧气/臭氧气体
流量：氧气＝500sccm，臭氧气体的浓度：100g/m3
处理时间：10秒
[第2吹扫工序]
吹扫气体：氩气
流量：500sccm
处理时间：10秒
接着，在第2成膜装置内中，在电容绝缘物102上层叠金属氧化物103(S12)。步骤S12是第3层叠工序的一例。在本实施方式中，金属氧化物103例如为氧化钨(WOx)。此外，作为其他方式，金属氧化物103例如可以为氧化钼(MoOx)、氧化钒(VOx)等。此外，金属氧化物103可以为包含钨(W)、钼(Mo)和钒(V)的氧化物。
另外，金属氧化物103还可以包含电容绝缘物102所含有的金属。例如在电容绝缘物102含有锆的情况下，金属氧化物103可以包含锆，在电容绝缘物102含有铪的情况下，金属氧化物103可以包含铪。
在步骤S12中，金属氧化物103例如通过ALD在电容绝缘物102上成膜。由此，例如如图4所示，在基材100上形成层叠有第1电极膜101、电容绝缘物102和金属氧化物103的被处理体W。然后，将被处理体W从第2成膜装置送出。
在步骤S12中的ALD中，被处理体W的温度例如为300℃，第2成膜装置内的压力例如为1Torr。此外，各工序的主要条件的一例如下所示。
[吸附工序]
原料：酰胺钨
处理时间：5秒
[第1吹扫工序]
吹扫气体：氩气
流量：500sccm
处理时间：10秒
[反应工序]
反应气体：氧气
流量：氧气＝500sccm
处理时间：10秒
[第2吹扫工序]
吹扫气体：氩气
流量：500sccm
处理时间：10秒
接着，将被处理体W送入退火装置内，在规定温度下对被处理体W进行退火(S13)。步骤S13是第1退火工序的一例。通过在规定温度下对被处理体W进行退火，电容绝缘物102的金属原子的一部分被金属氧化物103的金属原子的一部分置换，在电容绝缘物102与金属氧化物103的界面形成偶极子。由此，能够提高电容绝缘物102的势垒高度。
此处，退火的气氛必须为非还原气氛，但是并不一定必须为氧化气氛。退火的气氛例如优选氩气或氮气等非活性气氛。此外，在步骤S13中的退火的温度例如为400℃以下时，电容绝缘物102不结晶化。此外，在退火的温度例如为460℃以上时，电容绝缘物102的结晶化过度进行。因此，优选步骤S13中的退火例如在420℃以上450℃以下的范围内的温度下进行。
另外，在步骤S13中，例如为了在420℃以上450℃以下的范围内的温度下使电容绝缘物102适度地结晶化，优选在较低的温度下进行较长的时间的退火，在较高的温度下进行较短的时间的退火。例如在420℃下进行退火时，优选退火进行例如60分钟。此外，例如在450℃下进行退火时，优选退火进行例如2分钟。因此，优选将步骤S13中的退火进行例如2分钟以上60分钟以下的范围内的时间。
接着，将被处理体W送入第1成膜装置内，在金属氧化物103上层叠第2电极膜104(S14)。步骤S14是第4层叠工序的一例。在本实施方式中，第2电极膜104例如为氮化钛(TiN)。在步骤S14中，第2电极膜104例如通过使用钛的靶材在氮气气氛中进行的PVD(Physical Vapor Deposition：化学气相沉积)，在金属氧化物103上成膜。由此，例如如图5所示，在基材100上形成层叠有第1电极膜101、电容绝缘物102、金属氧化物103和第2电极膜104的被处理体W。然后，将被处理体W从第1成膜装置送出，本流程图所示的半导体装置的制造方法结束。
此处，为了与通过本实施方式的制造方法制造出的被处理体W相比，制作了在电容绝缘物102上层叠金属氧化物103，并在金属氧化物103上层叠了第2电极膜104后，对被处理体W进行了退火的比较例的被处理体。图6是表示研究了第2电极膜104是否存在膨胀的实验结果的一例的图。在图6所示的实验结果中，通过目视判断了是否存在膨胀。
例如如图6所示，在比较例的被处理体中，金属氧化物103的厚度为0.96～3.39nm时，在第2电极膜104发现了膨胀。在金属氧化物103的厚度为0.48nm时，目视下在第2电极膜104没有发现膨胀。但是，无论金属氧化物103的厚度为哪一厚度的情况下，在比较例的被处理体中，金属氧化物103都与第2电极膜104的紧贴性低，第2电极膜104容易脱落。
在比较例的被处理体中，在层叠第2电极膜104前不进行退火，在层叠了第2电极膜104后进行退火。由此，金属氧化物103由于退火而不仅与电容绝缘物102反应，还与第2电极膜104反应，在金属氧化物103和第2电极膜104之间局部地产生空隙。当在金属氧化物103与第2电极膜104之间局部地产生空隙时，在第2电极膜104发生膨胀，金属氧化物103与第2电极膜104之间的接触变得不充分。此外，当在金属氧化物103与第2电极膜104之间产生空隙时，金属氧化物103与第2电极膜104之间的紧贴性变低，第2电极膜104变得容易脱落。
对此，在通过本实施方式的制造方法制造出的被处理体W中，例如如图6所示，无论金属氧化物103为哪个厚度，都没有发现第2电极膜104的膨胀，金属氧化物103与第2电极膜104的紧贴性良好。
在本实施方式的半导体装置的制造方法中，在电容绝缘物102上层叠了金属氧化物103后，在金属氧化物103上层叠第2电极膜104前，对被处理体W进行退火。由此，能够抑制之后层叠于金属氧化物103上的第2电极膜104的膨胀和脱落。
以上，对第1实施方式进行了说明。半导体装置的制造方法包括第1层叠工序、第2层叠工序、第3层叠工序、第1退火工序和第4层叠工序。在第1层叠工序中，在基材100上层叠第1电极膜101。在第2层叠工序中，在第1电极膜101上层叠电容绝缘物102。在第3层叠工序中，在电容绝缘物102上层叠金属氧化物103。在第1退火工序中，对层叠于基材100上的第1电极膜101、电容绝缘物102和金属氧化物103进行退火。在第4层叠工序中，在进行了退火的金属氧化物103上层叠第2电极膜104。此外，电容绝缘物102是包含锆和铪中的至少任一者的氧化物，金属氧化物103是含有钨、钼和钒中的至少任一金属的氧化物。由此，能够抑制金属氧化物103上的第2电极膜104的膨胀和脱落。
另外，在上述的实施方式中，第1退火工序在非还原性气氛，优选氩气或者氮气等非活性气氛下，且在420℃以上450℃以下的范围内的温度下进行。由此，能够使电容绝缘物102适度地结晶化。
另外，在上述的实施方式中，也可以为，在电容绝缘物102包含锆的情况下，金属氧化物103还包含锆。此外，也可以为，在电容绝缘物102包含铪的情况下，金属氧化物103还包含铪。由此，能够高效地进行电容绝缘物102与金属氧化物103的界面的偶极子。
另外，在上述的实施方式中，第1电极膜101和第2电极膜104由氮化钛形成。由此，能够形成电容器。
[其他]
另外，本申请所公开的技术不限定于上述的实施方式，在其主旨的范围内能够进行多种变形。
例如，在上述的实施方式中，在金属氧化物103上层叠第2电极膜104前对被处理体W进行退火，但是本发明的技术不限于此。例如，可以在金属氧化物103上层叠了第2电极膜104后对被处理体W进一步进行退火。层叠了第2电极膜104后的退火，是第2退火工序的一例。由此，能够进一步提高电容绝缘物102的结晶性。此外，在形成第2电极膜104前，电容绝缘物102和金属氧化物103已经退火而形成为一体，因此，即使在层叠了第2电极膜104后对被处理体W进行退火，也不会发生第2电极膜104的膨胀和脱落。
另外，在上述的实施方式中的金属氧化物103的ALD中，反应工序中使用的气体能够采用氧气，但是公开的技术不限于此。例如，作为其他方式，在金属氧化物103的ALD的反应工序中，除了氧气之外，还可以使用臭氧气体。但是，在金属氧化物103的ALD的反应工序中，通过使用氧气而不使用臭氧气体，能够提高金属氧化物103的薄膜区域的膜厚控制性，例如能够形成
Figure BDA0002983802190000081
以下的薄膜。此外，在金属氧化物103的ALD的反应工序中，通过使用氧气而不使用臭氧气体，能够抑制因臭氧透过电容绝缘物102到达第1电极膜101而将第1电极膜101氧化的问题。
另外，在上述的实施方式中，第1电极膜101和第2电极膜104通过PVD成膜，但是成膜方法不限于此，也可以通过CVD(Chemical Vapor Deposition：化学气相沉积)、ALD等成膜。
另外，在上述的实施方式中，电容绝缘物102和金属氧化物103通过ALD成膜，但是成膜方法不限于此，也可以通过CVD等成膜。
另外，本次公开的实施方式在所有方面均是例示，而不应认为是限制性的。实际上，上述的实施方式能够以多种方式实现。此外，上述的实施方式在不脱离所附的权利要求的范围及其主旨的情况下，能够以各种方式省略、替换、改变
附图标记说明
W 被处理体
100 基材
101 第1电极膜
102 电容绝缘物
103 金属氧化物
104 第2电极膜。

Claims (5)

1.一种半导体装置的制造方法，其特征在于，包括：
在基材上层叠第1电极膜的第1层叠工序；
在所述第1电极膜上层叠电容绝缘物的第2层叠工序；
在所述电容绝缘物上层叠金属氧化物的第3层叠工序；
对层叠于所述基材上的所述第1电极膜、所述电容绝缘物和所述金属氧化物进行退火的第1退火工序；以及
在进行了退火的所述金属氧化物上层叠第2电极膜的第4层叠工序，
所述电容绝缘物是包含锆和铪中的至少任一者的氧化物，
所述金属氧化物是包含钨、钼和钒中的至少任一金属的氧化物。
2.如权利要求1所述的半导体装置的制造方法，其特征在于：
所述第1退火工序在非活性气氛下，且在420℃以上450℃以下的范围内的温度下进行。
3.如权利要求1或2所述的半导体装置的制造方法，其特征在于：
还包括第2退火工序，其在所述第4层叠工序后，对层叠于所述基材上的所述第1电极膜、所述电容绝缘物、所述金属氧化物和所述第2电极膜进行退火。
4.如权利要求1至3中任一项所述的半导体装置的制造方法，其特征在于：
在所述电容绝缘物含有锆的情况下，所述金属氧化物还包含锆，
在所述电容绝缘物含有铪的情况下，所述金属氧化物还包含铪。
5.如权利要求1至4中任一项所述的半导体装置的制造方法，其特征在于：
所述第1电极膜和所述第2电极膜由氮化钛形成。
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