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We have studied the adsorption, wetting, growth, and thermal evolution of the protic IL diethylmethylammonium trifluoromethanesulfonate ([dema][TfO]) on Au(111) and Ag(111). Ultrathin films were deposited at room temperature (RT) and at 90 K, and were characterized in situ by angle-resolved X-ray photoelectron spectroscopy. For both surfaces, we observe that independent of temperature, initially, a closed 2D wetting layer forms. While the film thickness does not increase past this wetting layer at RT, at 200 K and below, "moderate" 3D island growth occurs on top of the wetting layer. Upon heating, on Au(111), the [dema][TfO] multilayers desorb at 292 K, leaving an intact [dema][TfO] wetting layer, which desorbs intact at 348 K. The behavior on Ag(111) is much more complex. Upon heating [dema][TfO] deposited at 90 K, the [dema]+ cations deprotonate in two steps at 185 and 305 K, yielding H[TfO] and volatile [dema]0. At 355 K, the formed H[TfO] wetting layer partly desorbs (∼50%) and partly decomposes to form an F-containing surface species, which is stable up to 570 K.

We investigated the adsorption, surface enrichment, ion exchange, and on‐surface metathesis of ultrathin mixed IL films on Ag(111). We stepwise deposited 0.5 ML of the protic IL diethylmethylammonium trifluoromethanesulfonate ([dema][TfO]) and 1.0 ML of the aprotic IL 1‐methyl‐3‐octylimidazolium hexafluorophosphate ([C8C1Im][PF6]) at around 90 K. Thereafter, the resulting layered frozen film was heated to 550 K, and the thermally induced phenomena were monitored in situ by angle‐resolved X‐ray photoelectron spectroscopy. Between 135 and 200 K, [TfO]− anions at the Ag(111) surface are exchanged by [PF6]− anions and enriched together with [C8C1Im]+ cations at the IL/vacuum interface. Upon further heating, [dema][PF6] and [OMIm][PF6] desorb selectively at ∼235 and ∼380 K, respectively. Hereby, a wetting layer of pure [C8C1Im][TfO] is formed by on‐surface metathesis at the IL/metal interface, which completely desorbs at ∼480 K. For comparison, ion enrichment at the vacuum/IL interface was also studied in macroscopic IL mixtures, where no influence of the solid support is expected.