In this study, we have employed dual-color photoelectron emission microscopy (2P-PEEM) to visualize surface plasmon polaritons (SPPs) propagating along a chemically modified organic/metal interface of alkanethiolate self-assembled monolayers (Cn-SAMs; n is the number of alkyl carbon atoms) formed on Au(111). In dual-color 2P-PEEM, near-infrared photons around 900 nm generate SPPs at the Cn-SAMs/Au(111) interface, which interfere with the remaining light field. The resulting surface polarization beats are imaged as local distributions of 2P-photoelectrons probed by ultraviolet photons. Through dual-color 2P-PEEM for various alkyl chain lengths of Cn-SAMs, it is revealed that SPP properties are largely modified by an interfacial electronic state, particularly formed by the chemical interaction between surface Au atoms and adsorbate thiol molecules, thereby allowing the quantification of their group velocity at ∼0.86 times the speed of light. Since the SPP properties are controllable in terms of their height as organic dielectric layers, a bottom-up tailored technique using SAMs exhibits designer capability in adjusting the dielectric properties toward applications in surface plasmonic devices.

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Visualization of surface plasmon polariton (SPP) propagation at dielectric/metal interfaces is indispensable in providing opportunities for the precise designing and controlling of the functionalities of future plasmonic nanodevices. Here, we report the visualization of SPPs propagating along the buried organic/metal interface of fullerene (C 60 )/Au(111), through dual-colored two-photon photoemission electron microscopy (2P-PEEM) which precisely visualizes the SPP propagation of plasmonic metal nanostructures. Although SPPs excited by near-infrared photons at the few monolayer C 60 /Au(111) interface are clearly visualized as interference beat patterns between the SPPs and incident light, faithfully reflecting SPP properties modulated by the overlayer, photoemission signals are suppressed for thicker C 60 films, due to less valence electrons participating in 2P-photoemission processes. With the use of silver (Ag n (n = 21 and 55)) nanoclusters, which exhibit enhancement of overall photoemission intensities due to localized surface plasmons functioning as SPP sensitizers, it is revealed that the 2P-PEEM is applicable to the imaging of SPPs for thick C 60 /Au(111) interfaces, where SPP properties are hardly modulated by the added small amount (∼0.1 monolayer) of Ag n sensitizers.

We have employed a two-photon photoelectron emission microscopy (2P-PEEM) to observe the photocarrier electron dynamics in an organic thin film of fullerene (C60) formed on a highly oriented pyrolytic graphite with a spatial resolution of ca. 135 nm. In this approach, photocarrier electrons in C60 single-layer islands generated by the first pump photon are detected by the second probe photon. These spectromicroscopic observations conducted over a 100 × 100 nm2 region of C60 islands consistently reproduced the macroscopic two-photon photoemission spectrum of fully covered C60 monolayer film, where the energy of photocarrier electron in the islands was +0.9 eV relative to the Fermi level. Time-resolved 2P-PEEM revealed that the photocarrier electron decayed from the monolayered C60 islands into the substrate with a time constant of 470 ± 30 fs.