With the recent developments in secondary ion mass spectrometry (SIMS), it is now possible to obtain molecular depth profiles and 3D molecular images of organic thin films, i.e. SIMS depth profiles where the molecular information of the mass spectrum is retained through the sputtering of the sample. Several approaches have been proposed for "damageless" profiling, including the sputtering with SF and C clusters, low energy Cs ions and, more recently, large noble gas clusters (Ar). In this article, we evaluate the merits of these different approaches for the in depth analysis of organic photovoltaic heterojunctions involving poly(3-hexylthiophene) (P3HT) as the electron donor and [6,6]-phenyl C butyric acid methyl ester (PCBM) as the acceptor. It is demonstrated that the use of 30 keV C and 500 eV Cs (500 eV per atom) leads to strong artifacts for layers in which the fullerene derivative PCBM is involved, related to crosslinking and topography development. In comparison, the profiles obtained using 10 keV Ar (∼6 eV per atom) do not indicate any sign of artifacts and reveal fine compositional details in the blends. However, increasing the energy of the Ar cluster beam beyond that value leads to irreversible damage and failure of the molecular depth profiling. The profile qualities, apparent interface widths and sputtering yields are analyzed in detail. On the grounds of these experiments and recent molecular dynamics simulations, the discussion addresses the issues of damage and crater formation induced by the sputtering and the analysis ions in such radiation-sensitive materials, and their effects on the profile quality and the depth resolution. Solutions are proposed to optimize the depth resolution using either large Ar clusters or low energy cesium projectiles for sputtering and/or analysis.
Mouhib, T., Poleunis, C., Wehbe, N., Michels, J. J., Galagan, Y., Houssiau, L., ... Delcorte, A. (2013). Molecular depth profiling of organic photovoltaic heterojunction layers by ToF-SIMS: Comparative evaluation of three sputtering beams. Analyst, 138(22), 6801-6810. https://doi.org/10.1039/c3an01035j