CN113388825A - 氮化钛膜制备方法和装置 - Google Patents
氮化钛膜制备方法和装置 Download PDFInfo
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- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 44
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 31
- 239000010703 silicon Substances 0.000 claims abstract description 31
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000460 chlorine Substances 0.000 claims abstract description 17
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 17
- 238000010926 purge Methods 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 239000011261 inert gas Substances 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000010936 titanium Substances 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- 238000005086 pumping Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000000376 reactant Substances 0.000 claims abstract description 12
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 9
- 238000005121 nitriding Methods 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- -1 hydrogen ions Chemical class 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000006227 byproduct Substances 0.000 claims abstract description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 3
- 239000010408 film Substances 0.000 description 43
- 238000010586 diagram Methods 0.000 description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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Abstract
本发明公开了一种氮化钛膜制备方法，通过原子层沉积法在硅片上沉积氮化钛膜，采用多次循环形成所述氮化钛膜，所述多次循环包括以下步骤：S1，在腔体内放入硅片，通过第一气体管路通入钛原料气体，使其与所述硅片的硅衬底发生化学吸附，直至所述硅衬底表面达到饱和；S2，通入惰性气体进行吹扫，将过剩的反应物从系统中抽出清除；S3，通入氢离子到所述腔体内，与所述硅衬底中残留的氯反应形成氯化氢气体；S4，通入惰性气体进行吹扫，将过剩的反应物从系统中抽出清除；S5，通过第二气体管路通入氮化气体，使之和所述衬底上被吸附的所述钛原料发生反应；S6，通入惰性气体进行吹扫，将过剩的反应物和反应副产品从系统中抽出清除。
Description
技术领域
本发明涉及一种半导体集成电路的制造方法，特别是涉及一种氮化钛膜制备方法和装置。
背景技术
在半导体器件的制造中，氮化钛(TiN)由于良好的导电性，良好的热稳定性成为半导体器件领域多用途材料。如氮化钛作为扩散阻挡层防止钨扩散到氧化层和硅衬底，同时在HKMG(high-k metal-gate)工艺中氮化钛也作为附着层附着于氧化层表面，用于金属栅电极层等用途。
氮化钛膜采用ALD成膜方法具有良好的阶梯覆盖层被广泛应用。ADL氮化钛膜的成膜方法是通过交替供给原料气体四氯化钛(TiCl4)气体和作为氮化气体的氨气(NH3)，通过将其反复规定次数，形成规定膜厚的氮化钛膜。
在现有技术中，氮化钛膜的厚度在不断减薄，常用2～3nm以下的极薄膜，专利文献CN107978541A报道，通过使用TiCl4气体和NH3气体的ALD法成膜氮化钛膜时，存在膜厚越薄而膜中的氯残留浓度越高的趋势。主要是因为膜厚越薄，膜厚中残留的氯浓度比例相对变高。由于该残留氯浓度的比例高，会导致薄氮化钛膜与厚氮化钛膜相比电阻率变大，特别是在膜厚1.5nm以下的极薄膜中，残留氯的比例较高。如图1所示。
通常是通过增加NH3气体的流量，能够使残留的氯浓度降低，但是通过排气泵的能力而流过的流量有限制，与残留氯反应的数量有限，难以获得充分的降低残留氯浓度的效果。
发明内容
本发明所要解决的技术问题是，如何使膜厚减薄的氮化钛膜中，降低含氯浓度，形成低电阻率的氮化钛膜。
本发明提供一种氮化钛膜制备方法，通过原子层沉积法在硅片上沉积氮化钛膜，采用多次循环形成所述氮化钛膜，所述多次循环包括以下步骤：
S1，在腔体内放入硅片，通过第一气体管路通入钛原料气体，使其与所述硅片的硅衬底发生化学吸附，直至所述硅衬底表面达到饱和；
S2，通入惰性气体进行吹扫，将过剩的反应物从系统中抽出清除；
S3，通入氢离子到所述腔体内，与所述硅衬底中残留的氯反应形成氯化氢气体；
S4，通入惰性气体进行吹扫，将过剩的反应物从系统中抽出清除；
S5，通过第二气体管路通入氮化气体，使之和所述衬底上被吸附的所述钛原料发生反应；
S6，通入惰性气体进行吹扫，将过剩的反应物和反应副产品从系统中抽出清除。
可选地，所述步骤S1中，所述钛原料气体为四氯化钛。
可选地，所述步骤S5中，所述氮化气体为氨气。
可选地，所述惰性气体为氮气。
可选地，所述硅片的成膜温度控制为300℃至550℃范围。
可选地，所述步骤S2、S4、S6的所述吹扫的时间为5至8秒。
本发明还提供一种氮化钛膜制备装置，通过原子层沉积法在硅片上沉积氮化钛膜，采用如权利要求1至6中任一项的所述氮化钛膜制备方法。
本发明还提供一种存储介质，其存储有在计算机上运行的用于控制氮化钛膜制备方法的程序，所述程序使计算机控制执行如权利要求1至6中任一项的所述氮化钛膜制备方法。
本发明与现有技术相比，无需使NH3气体的流量增加，就可以得到残留氯的去除效果，即使是薄氮化钛膜，也能够降低膜中的氯浓度。从而降低电阻率。另外，为了得到同样的电阻率，NH3气体的流量能够比现有技术中变少。
附图说明
图1为现有技术氮化钛膜中氯浓度示意图。
图2为具体实施方案的循环步骤示意图。
图3为具体实施方案与现有技术对比示意图。
具体实施方式
实施例1
本实施例的氮化钛膜制备方法，通过原子层沉积法(Atomic Layer Deposition；ALD法)在硅片上沉积氮化钛膜，采用多次循环形成所述氮化钛膜。循环次数可以根据所需的氮化钛膜厚度确定。图2为本发明具体实施方案的循环步骤示意图。多次循环包括以下步骤：
步骤S1，在腔体内放入硅片，通过第一气体管路通入钛原料气体TiCl4，使其与所述硅片的硅衬底发生化学吸附，压力：2～10Torr(267～1333Pa)，成膜温度(硅片温度)：300～550℃，TiCl4气体流量：0.3slm～1.5slm，直至所述硅衬底表面达到饱和，T1的时间(每一次)：1～5sec；
S2，通入惰性气体氮气进行吹扫，N2气体流量(合计)：1slm～10slm，T2(吹扫)的时间(每一次)：5～8sec，将过剩的反应物从系统中抽出清除；
S3，通入氢离子到所述腔体内，H2气体流量：0.1slm～1slm，与所述硅衬底中残留的氯反应形成氯化氢气体，T3的时间(每一次)：1～5sec；
S4，通入惰性气体氮气进行吹扫，N2气体流量(合计)：1slm～10slm，T4(吹扫)的时间(每一次)：5～8sec，将过剩的反应物从系统中抽出清除；
S5，通过第二气体管路通入氮化气体氨气，NH3气体流量：1slm～9slm，使之和所述衬底上被吸附的所述钛原料发生反应，T5的时间(每一次)：5～15sec；
S6，通入惰性气体进行吹扫，N2气体流量(合计)：1slm～10slm，T6(吹扫)的时间(每一次)：5～8sec，将过剩的反应物和反应副产品从系统中抽出清除。
本实施例在每一个循环中，在通入Ticl4通入之后，通入氢离子与氮化钛膜中残留的氯反应形成HCL气体，之后被清除，形成含氯较少的氮化钛膜，改善了氮化钛膜电阻率。
实施例2
本实施例为一种氮化钛膜制备装置，通过原子层沉积法在硅片上沉积氮化钛膜，采用如实施例1的氮化钛膜制备方法。
实施例3
本实施例为一种存储介质，其存储有在计算机上运行的用于控制氮化钛膜制备方法的程序，所述程序使计算机控制执行如实施例1的氮化钛膜制备方法。
以上通过具体实施方式和实施例对本发明进行了详细的说明，但这些并非构成对本发明的限制。在不脱离本发明原理的情况下，本领域的技术人员还可做出许多变形和改进，这些也应视为本发明的保护范围。
Claims (8)
1.一种氮化钛膜制备方法，通过原子层沉积法在硅片上沉积氮化钛膜，其特征在于，采用多次循环形成所述氮化钛膜，所述多次循环包括以下步骤：
S1，在腔体内放入硅片，通过第一气体管路通入钛原料气体，使其与所述硅片的硅衬底发生化学吸附，直至所述硅衬底表面达到饱和；
S2，通入惰性气体进行吹扫，将过剩的反应物从系统中抽出清除；
S3，通入氢离子到所述腔体内，与所述硅衬底中残留的氯反应形成氯化氢气体；
S4，通入惰性气体进行吹扫，将过剩的反应物从系统中抽出清除；
S5，通过第二气体管路通入氮化气体，使之和所述衬底上被吸附的所述钛原料发生反应；
S6，通入惰性气体进行吹扫，将过剩的反应物和反应副产品从系统中抽出清除。
2.如权利要求1所述的氮化钛膜制备方法，其特征在于：
所述步骤S1中，所述钛原料气体为四氯化钛。
3.如权利要求1所述的氮化钛膜制备方法，其特征在于：
所述步骤S5中，所述氮化气体为氨气。
4.如权利要求1所述的氮化钛膜制备方法，其特征在于：
所述惰性气体为氮气。
5.如权利要求1所述的氮化钛膜制备方法，其特征在于：
所述硅片的成膜温度控制为300℃至550℃范围。
6.如权利要求1所述的氮化钛膜制备方法，其特征在于：
所述步骤S2、S4、S6的所述吹扫的时间为5至8秒。
7.一种氮化钛膜制备装置，通过原子层沉积法在硅片上沉积氮化钛膜，其特征在于：
采用如权利要求1至6中任一项的所述氮化钛膜制备方法。
8.一种存储介质，其存储有在计算机上运行的用于控制氮化钛膜制备方法的程序，其特征在于：
所述程序使计算机控制执行如权利要求1至6中任一项的所述氮化钛膜制备方法。
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| CN1841676A (zh) * | 2005-03-28 | 2006-10-04 | 东京毅力科创株式会社 | 使用原子层沉积法的氮化硅膜的形成方法 |
| US20150110959A1 (en) * | 2013-10-18 | 2015-04-23 | Tokyo Electron Limited | Film forming method and film forming apparatus |
| CN107868944A (zh) * | 2017-10-31 | 2018-04-03 | 北京北方华创微电子装备有限公司 | 一种氮化钛原子层沉积装置及其沉积方法 |
| CN110468388A (zh) * | 2019-09-25 | 2019-11-19 | 上海华力微电子有限公司 | 原子层沉积法形成氮化物膜的方法 |
| CN110578130A (zh) * | 2018-06-08 | 2019-12-17 | 东京毅力科创株式会社 | 成膜方法及成膜装置 |
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| CN1841676A (zh) * | 2005-03-28 | 2006-10-04 | 东京毅力科创株式会社 | 使用原子层沉积法的氮化硅膜的形成方法 |
| US20150110959A1 (en) * | 2013-10-18 | 2015-04-23 | Tokyo Electron Limited | Film forming method and film forming apparatus |
| CN107868944A (zh) * | 2017-10-31 | 2018-04-03 | 北京北方华创微电子装备有限公司 | 一种氮化钛原子层沉积装置及其沉积方法 |
| CN110578130A (zh) * | 2018-06-08 | 2019-12-17 | 东京毅力科创株式会社 | 成膜方法及成膜装置 |
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