Scaling Dependencies in Irradiation-Driven Molecular Dynamics Simulations: Case Study of W(CO)$_6$ Fragmentation

TL;DR

This study uses irradiation-driven molecular dynamics to analyze how W(CO)$_6$ molecules fragment under electron irradiation, revealing dependencies on precursor density and irradiation conditions, and providing scaling relations for better simulation accuracy.

Contribution

It introduces scaling relations linking irradiation parameters to fragmentation outcomes in IDMD simulations of W(CO)$_6$, enhancing the quantitative modeling of FEBID processes.

Findings

Fragmentation depends on precursor density and electron fluence.

Higher densities and fluences lead to more tungsten cluster formation.

Steady states with stable fragment distributions can be achieved.

Abstract

Irradiation-driven fragmentation and chemical transformations of organometallic molecules play a central role in nanofabrication techniques based on the use of focused charged-particle beams. In this paper, the electron irradiation-induced fragmentation dynamics of W(CO)$_6$, a commonly used precursor for focused electron beam-induced deposition (FEBID), is investigated using the irradiation-driven molecular dynamics (IDMD) method. Simulations are performed for gas-phase systems with different precursor densities and under different irradiation conditions. The results reveal progressive fragmentation of W(CO)$_6$ molecules into W(CO)$_n$ species, accompanied by the formation of W-rich molecular clusters. The evolution of fragment abundances shows a strong dependence on both precursor density and electron fluence. Higher densities and larger fluences result in more extensive fragmentation and promote the aggregation of tungsten atoms into small metal clusters. Under certain irradiation conditions, the studied molecular systems evolve towards a steady state characterised by slightly varying fragment abundances. The obtained scaling relations between irradiation parameters and fragment distributions provide guidance for selecting simulation parameters in IDMD simulations of the FEBID process, ensuring a quantitative description of precursor fragmentation dynamics.