Nonadiabatic dynamics of cobalt tricarbonyl nitrosyl for ligand dissociation induced by electronic excitation

Yeonghun Lee,Grigory Kolesov,Kyeongjae Cho,Xiaolong Yao,Efthimios Kaxiras

doi:10.1038/s41598-021-88243-2

Yeonghun Lee, Grigory Kolesov + Show 3 more

Open Access

https://doi.org/10.1038/s41598-021-88243-2

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Abstract

We utilize real-time time-dependent density functional theory and Ehrenfest dynamics scheme to investigate excited-state nonadiabatic dynamics of ligand dissociation of cobalt tricarbonyl nitrosyl, Co(CO)3NO, which is a precursor used for cobalt growth in advanced technologies, where the precursor’s reaction is enhanced by electronic excitation. Based on the first-principles calculations, we demonstrate two dissociation pathways of the NO ligand on the precursor. Detailed electronic structures are further analyzed to provide an insight into dynamics following the electronic excitations. This study sheds light on computational demonstration and underlying mechanism of the electronic-excitation-induced dissociation, especially in molecules with complex chemical bonds such as the Co(CO)3NO.

Highlights

We utilize real-time time-dependent density functional theory and Ehrenfest dynamics scheme to investigate excited-state nonadiabatic dynamics of ligand dissociation of cobalt tricarbonyl nitrosyl, Co(CO)3NO, which is a precursor used for cobalt growth in advanced technologies, where the precursor’s reaction is enhanced by electronic excitation
In addition to the enhanced atomic layer deposition (EE-ALD), the energetic electrons can be exploited for focused electron beam induced deposition (FEBID), which is a useful technique for nanopatterning on solid surfaces[5]
To explore excited-state nonadiabatic dynamics, we carry out ab initio molecular dynamics study employing the time-dependent density functional theory (TDDFT)-MD based on Ehrenfest dynamics, which has been implemented in a computational package, TDAP-2.0 (Time-evolving Deterministic Atom Propagator)[28,29,30,31,32] based on the SIESTA33 package

Summary

Introduction

We utilize real-time time-dependent density functional theory and Ehrenfest dynamics scheme to investigate excited-state nonadiabatic dynamics of ligand dissociation of cobalt tricarbonyl nitrosyl, Co(CO)3NO, which is a precursor used for cobalt growth in advanced technologies, where the precursor’s reaction is enhanced by electronic excitation. The scaling limit for the current complementary metal–oxide semiconductor (CMOS) technology necessitates a three-dimensional integration with vertically stacked electronic components[1] This requires low thermal budget processes in order to prevent the degradation of devices and interconnects underneath the top layer undergoing thermal processes. This work elucidates the atomic and electronic processes that constitute the excitation-driven dissociation of ligands on Co(CO)3NO using the first-principles calculation based on the density functional theory (DFT)[21,22]. We locate direct dissociation channels, providing an insight into the excitation-driven unimolecular dissociation of the Co(CO)3NO

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Conclusion