AbstractToday, several methods are used for secondary ion yield enhancement in time‐of‐flight SIMS (ToF‐SIMS). Some deal with the modification of sample properties, e.g. with monolayer preparation of analytes on metal substrates instead of thick layers, or the metalization of thick‐layer samples with noble metals like gold or silver (MetA‐SIMS). Other methods deal with primary ion beam parameters, e.g. the use of heavier ions or the use of polyatomic instead of monoatomic primary ions.To investigate the yield‐enhancing effects of the combination of these techniques, (sub‐) monolayers of polyethylene imine, both pristine and metalized with different amounts of gold, were prepared on substrate materials with different stopping powers. For primary ion (PI) bombardment, monoatomic (Ne+, Ar+, Kr+, Xe+, Bi+) and polyatomic (Bin+, Bin++) primary ions were used.It was found that all techniques used in this contribution increase the secondary ion yield mainly by increasing the stopping power, thereby increasing the amount of PI energy that is deposited near the sample surface (upper 5 nm). Only a small additional yield enhancement was observed when to a yield‐enhancing technique such as polyatomic PI bombardment, which deposits nearly all the PI energy near the surface, another technique was added that is based on the same mechanism for yield enhancement. In other words, the yield enhancement achieved by two enhancement techniques used in combination was much smaller than the product of the yield enhancements obtainable with each technique taken by itself. Copyright © 2010 John Wiley & Sons, Ltd.
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