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Atomic Layer Deposition of Pt on the Surface Deactivated by Fluorocarbon Implantation: Investigation of the Growth Mechanism
Chemistry of Materials ( IF 7.2 ) Pub Date : 2020-11-04 , DOI: 10.1021/acs.chemmater.0c03372
Woo-Hee Kim 1, 2 , Kihyun Shin 3, 4 , Bonggeun Shong 5 , Ludovic Godet 6 , Stacey F. Bent 1
Affiliation  

Selective atomic layer deposition (ALD) using surface-controlled reactivity is attracting a great deal of attention as a simple bottom-up patterning process that can provide both continued dimensional scaling and accurate pattern placement for next-generation nanoelectronics. We previously reported topographically selective deposition through Pt ALD using a MeCpPtMe3 precursor and an O2 counter reactant on fluorocarbon (CFx)-modified surfaces; however, gradual loss of selectivity in the CFx-modified regions was observed during the Pt ALD process. This work develops a fundamental understanding of the microscopic growth mechanisms of Pt ALD on the CFx-modified surface using a combination of experimental analyses and theoretical methods. The Pt growth characteristics on the CFx surface are investigated within a temperature window from 225 to 350 °C, and the results show a sharp sensitivity to growth temperature, with significant Pt growth occurring at temperatures above 300 °C. Through density functional theory (DFT) calculations, the reaction energies for adsorption of oxygen and the MeCpPtMe3 precursor as well as formation of reaction products of CFx degradation are determined. Based on experimental results in conjunction with the DFT calculations, we show that while lower temperature Pt ALD (<300 °C) on CFx-modified surfaces can be significantly retarded because of a lack of MeCpPtMe3 chemisorption, the surface reaction pathways for Pt ALD on CFx-modified surfaces at temperatures above 300 °C can proceed through oxygen adsorption and CF4 desorption followed by Pt nucleation in CFx-degraded regions.

中文翻译:

氟碳注入钝化表面上Pt的原子层沉积:生长机理的研究

使用表面受控反应性的选择性原子层沉积(ALD)作为一种简单的自下而上的图案化工艺吸引了众多关注,该工艺可以为下一代纳米电子产品提供连续的尺寸缩放和精确的图案放置。我们先前报道了在MecpPtMe 3前驱体和O 2抗衡反应物在碳氟化合物(CF x)改性的表面上通过Pt ALD进行的选择性沉积。然而,在Pt ALD过程中观察到了CF x修饰区域中选择性的逐渐损失。这项工作对CF x上Pt ALD的微观生长机理有了基本的了解。结合实验分析和理论方法对表面进行改性。在225至350°C的温度范围内研究了CF x表面上Pt的生长特性,结果表明对生长温度具有敏锐的敏感性,在高于300°C的温度下会显着生长Pt。通过密度泛函理论(DFT)计算,确定了吸附氧和MeCpPtMe 3前体的反应能以及CF x降解反应产物的形成。基于实验结果和DFT计算,我们发现CF x上的较低温度Pt ALD(<300°C)由于缺少MeCpPtMe 3的化学吸附作用,改性后的表面会明显受阻,温度高于300°C时,CF x改性后的表面上Pt ALD的表面反应途径可通过氧吸附和CF 4解吸,然后在CF中形成Pt成核来进行x退化的区域。
更新日期:2020-11-25
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