The assembly of Ag and Au nanoparticles (NPs) into nanoparticulate arrays mediated by terpyridine (tpy), 4'-(2-thienyl)terpyridine (T-tpy), and short α,ω-bis(tpy)oligothiophene ligands has been accomplished at the interface between the Ag or Au NP hydrosol and a solution of the molecular species in dichloromethane. The relationship between the morphology and the optical responses of the arrays has been investigated by advanced methods of TEM (transmission electron microscopy) image analysis and surface plasmon extinction (SPE) spectra. It has been established that the size of islands of closely spaced NPs rather than the average interparticle distance affects the extent of delocalization of the surface plasmon excitations and thus also the SPE spectra. Furthermore, the structure of surface-adsorbate complexes formed in these arrays has been investigated by SERS spectral measurements carried out as a function of the excitation wavelength. Photoinduced charge transfer (CT) transitions from the neutral Ag and Au adsorption sites on metal NPs to antibonding orbitals of the adsorbates have been identified for Ag/tpy, Ag/T-tpy, Au/tpy, and Au/T-tpy nanoparticulate arrays. Although the surface-adsorbate complexes displaying a photoinduced CT are known for Ag NPs, the Au surface complexes with this CT are newly reported. Bis(tpy)oligothiophenes were found to be attached to both Ag and Au NPs via the tpy group(s). The match between the interparticle distances within the NP islands and the lengths of the oligomers molecules indicates that the molecules act as interparticle linkers. In this case, unequivocal spectral marker band evidence of the Ag as well as Au surface complex formation has not been obtained.

Single layer graphene (SLG) and two-dimensional (2-D) plasmonic Ag nanoparticle arrays assembled by chemisorption of ethanethiol (ET) molecules (AgNPs-ET) were employed as components of two types of hybrid systems designed for surface-enhanced Raman scattering (SERS) spectral probing of SLG localized in the vicinity of plasmonic NPs. Both hybrids were characterized by optical microscopy, transmission electron microscopy (TEM), surface plasmon extinction (SPE), and SERS microRaman spectral measurements at four excitation wavelengths spanning the 445-780 nm range. SERS spectral probing of the glass/SLG/AgNPs-ET hybrid prepared by overdeposition of SLG on glass by the array of ET-modified Ag NPs has shown that the chemisorbed ET acts as an efficient molecular spacer between SLG and Ag NPs surface which, in turn, enabled to obtain SERS spectra of SLG unperturbed by doping or strain. TEM imaging and SERS spectral probing of the second hybrid prepared by overdeposition of AgNPs-ET array on glass by SLG revealed removal of the adsorbed ET molecules and annealing of Ag NPs during the SLG deposition. The characteristics of the resulting glass/AgNPs/SLG hybrid system, namely (i) broad distribution of the annealed Ag NPs sizes and shapes, (ii) SPE curve covering the overall visible spectral region, (iii) absence of the ET spectral bands in SERS spectra, and (iv) fairly uniform SERS enhancement of the G and 2D mode of SLG in the 532-780 nm range in the straight sample geometry indicate that this hybrid can provide a suitable platform for investigation of the excitation wavelength dependence of combined SERS/GERS (graphene-enhanced Raman scattering) enhancement experienced by various molecular species brought into contact with SLG in this hybrid. Finally, weak optical effects attributed to increased reflectivity of SLG in the near field of Ag NPs arrays have been observed in the excitation wavelength dependence of the SERS spectra of both types of hybrid systems.

Hybrid systems constituted by plasmonic nanostructures and single-layer graphene (SLG) as well as their employment as platforms for surface-enhanced Raman scattering (SERS) of the molecular species have recently become a subject of interest. By contrast, only a few studies were targeted specifically on the combination of SERS with graphene-enhanced Raman scattering (GERS) of aromatic molecules. In this paper, we have investigated the mechanisms of combined SERS + GERS by micro-Raman spectral mapping of the hybrid system constituted by annealed Ag nanoparticles (NPs) on the glass substrate overdeposited first by SLG and, subsequently, by a monolayer (ML) of free-base phthalocyanine (H 2 Pc) molecules, as well as of glass/SLG/ H 2 Pc(ML) and of graphite/H 2 Pc(ML) reference systems. Raman mapping was performed at multiple excitation wavelengths spanning the 532−830 nm range and was complemented by surface plasmon extinction and transmission electron microscopy images of the Ag NP platform. Observation of SERS + GERS in the aforementioned hybrid system was established by the determination of GERS, SERS, and SERS + GERS enhancement factors. By construction and the mutual comparison of GERS + SERS and GERS excitation profiles of H 2 Pc vibrational modes, operation of two mechanisms of GERS additively with the electromagnetic SERS enhancement in SERS + GERS of H 2 Pc in the glass/Ag NPs/SLG/H 2 Pc(ML) hybrid system has been ascertained. Finally, achievement of the same level of the weak negative doping of SLG by Ag NPs in the probed hybrid system and by glass in the reference system has been established as a necessary condition for the proper evaluation of mechanisms of combined SERS and GERS, and evidence for the fulfillment of this condition in the hybrid systems reported here was provided.

Adsorbate‐containing, nanosponge Ag aggregates overlayed by a thin (~1.5 mm) liquid layer are reported as a new type of sample for Surface‐enhanced Raman scattering (SERS) microRaman spectral measurements and adsorbate (analyte) detection. Macroscopic Ag aggregates (of about 1.5 × 1.0 × 0.025 mm size) with the nanosponge internal morphology (revealed by Scanning electron microscopy (SEM)) were prepared by 3D assembling of fused fractal aggregates (D = 1.84 ± 0.04) formed in Ag nanoparticle hydrosol/HCl/adsorbate systems with 2,2’‐bipyridine (bpy) and/or a cationic free‐base tetrakis(2‐methyl‐4‐pyridiniumyl) porphine (H2TMPyP) as the testing adsorbates. For SERS microRaman measurements, the macroscopic aggregate was overlayed by a thin (~1.5 mm) layer of the residual liquid. Preparation procedure, nanoscale imaging, and SERS spectral probing including the determination of the detection limits of the adsorbates revealed the following advantages of the adsorbate‐containing, liquid‐overlayed 3D nanosponge aggregate as a sample for SERS microRaman spectral measurements: (1) localization of adsorbate (analyte) into hot spots and, simultaneously, prevention of the analyte decomposition during the spectral measurement (carried out without an immersion objective), (2) fast and simple sample preparation, and (3) minimization of sample volume and an efficient concentration of hot spots into the focus of the laser beam. The advantages of the nanosponge Ag aggregates are further demonstrated by the 40 fmol limit of detection of bpy as Ag(0)‐bpy surface complex, as well as by preservation of the native structure of the cationic free‐base porphyrin H2TMPyP. Copyright © 2015 John Wiley & Sons, Ltd.