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

Journal Article · Mon Nov 10 00:00:00 UTC 2025 · ACS Applied Materials and Interfaces

DOI: https://doi.org/10.1021/acsami.5c14331 · OSTI ID:3007641

Shaw, Santosh ^[1]; Silva, Tiago  ^[2]; Bobbitt, Jonathan M. ^[3]; Naab, Fabian ^[4]; Rodrigues, Cleber L. ^[2]; Smith, Emily A.  ^[3]; Cademartiri, Ludovico  ^[5]

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1. Iowa State Univ., Ames, IA (United States)
2. Univ. of Sao Paulo (Brazil)
3. Ames Lab., and Iowa State Univ., Ames, IA (United States)
4. Univ. of Michigan, Ann Arbor, MI (United States)
5. Univ. of Parma (Italy)

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.

• Research Organization: Ames Laboratory (AMES), Ames, IA (United States)
• Sponsoring Organization: Semiconductor Research Corporation; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
• Grant/Contract Number: AC02-07CH11358
• OSTI ID: 3007641
• Journal Information: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 46 Vol. 17; ISSN 1944-8244; ISSN 1944-8252
• Publisher: American Chemical Society (ACS)Copyright Statement
• Country of Publication: United States
• Language: English