AVS 60th International Symposium and Exhibition
    Applied Surface Science Monday Sessions
       Session AS+BI-MoM

Invited Paper AS+BI-MoM10
Why is Low Energy Cesium so Efficient for Depth-profiling Organics?

Monday, October 28, 2013, 11:20 am, Room 204

Session: Organic Depth Profiling
Presenter: L. Houssiau, University of Namur, Belgium
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Organic materials are known to be very sensitive to ion bombardment, mostly owing to free radical creation upon etching, leading to many chemical reactions like hydrogen abstraction, double bond creation and crosslinking. Most organics eventually degrade into a graphitized material, with no memory left of the initial material’s chemistry. However, this picture has dramatically evolved over the last decade thanks to breakthrough developments in the field of molecular depth profiling. It started with the use of polyatomic ion sources (SF5+, C60+), followed by massive Arn+ clusters which are now considered as standards for molecular depth profiling. Those cluster sources exhibit a sputtering yield high enough to sputter molecular damages away. Our group has followed a thoroughly different approach since 2007, when we showed that, surprisingly, low energy (~250 eV) Cs+ ions could also be used to depth profile polymers. We have extended the study to many different organic materials, including amino acid thin films, analyzed in the energy range 150-1000 eV. So far, it appears that most organics are amenable to depth-profiling with this method, making it a complementary approach to cluster ion beams. We will review our understanding on how low energy Cs+ ions prevent material degradation. Cs+ ions are neutralized as soon as they hit the surface, for electrostatic reasons, leaving implanted Cs atoms in the subsurface region. Cs being an extremely reactive element quickly reacts with free radicals generated by ion impact, preventing cross-linking reactions, thus allowing molecular depth profiling. This reaction goes along with a strong negative ionization, as an electron is transferred from the alkali to the molecule. Indeed, negative molecular ion detection in ToF-SIMS experiments is much increased with respect to inert ions. Our model is supported by XPS data, showing changes in the charge state of various molecules (amino acids, polymers) irradiated with Cs+ ions. Moreover, the existence of neutral cesium at the surface was detected by optical emission spectroscopy measurements. We will present our most recent data on Phenylalanine delta layers embedded in a Tyrosine matrix, on which a depth resolution below 5 nm was observed. We will also discuss the decisive influence of the analysis beam (i.e. Ga+ or Bi3+) in a ToF-SIMS dual beam experiment. Besides its fundamental interest, low energy Cs+ sputtering appears to be an efficient tool to depth profile both organics and inorganics. Its major assets are a high negative ion signal combined with an excellent depth resolution.