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Dehydrogenation vs Apparent Hydrogenation: Unraveling the Mechanisms of He and O2 Plasma Etching on Colloidal Nanocrystal Films

Santosh Shaw,T. Silva,J. Bobbitt,F. Naab,C. L. Rodrigues,Emily A. Smith,L. Cademartiri

Published 2025 in ACS Applied Materials and Interfaces

ABSTRACT

Removing organic ligands from colloidal nanoparticles is critical for fabricating solid-state devices, yet accurately quantifying this removal remains a significant analytical challenge. Here, we establish a robust and accessible method for this quantification by calibrating Raman spectroscopy against precise ion beam analysis (IBA) for nanoparticle assemblies (CNAs) processed by helium (He) and oxygen (O2) plasmas. We demonstrate that the calibration curves are remarkably independent of plasma power and pressure, depending critically only on the choice of feed gas. He plasma induces rapid dehydrogenation and cross-linking, evidenced by a much faster decrease in the C–H Raman signal relative to the actual carbon loss. Conversely, O2 plasma leads to a surprising “apparent hydrogenation”, where the carbon backbone is removed significantly faster than the C–H signal diminishes. This counterintuitive effect is explained by a serial mechanism of oxidative fragmentation; β-scission cleaves the alkyl chains, and subsequent stabilization steps enrich the remaining film with hydrogen-rich methyl-terminated fragments, while carbon is efficiently removed as volatile CO. This work provides calibrated functions that enable the rapid determination of absolute carbon content in processed CNAs using simple Raman spectroscopy with uncertainties of ∼8% for O2 and ∼12% for He plasma, offering a vital tool for both process diagnostics and fundamental studies of plasma–matter interactions in colloidal nanocrystal films.

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