A longstanding challenge in nanoparticle characterization is to understand anisotropic distributions of organic ligands at the surface of inorganic nanoparticles. Here, we show that using electron energy loss spectroscopy in an aberration-corrected scanning transmission electron microscope we can directly visualize and quantify ligand distributions on gold nanorods (AuNRs). These experiments analyze dozens of particles on graphene substrates, providing insight into how ligand binding densities vary within and between individual nanoparticles. We demonstrate that the distribution of cetyltrimethylammonium bromide (CTAB) on AuNRs is anisotropic, with a 30% decrease in ligand density at the poles of the nanoparticles. In contrast, the distribution of (16-mercaptohexadecyl)­trimethylammonium bromide (MTAB) is more uniform. These results are consistent with literature reported higher reactivity at the ends of CTAB-coated AuNRs. Our results demonstrate the impact of electron spectroscopy to probe molecular distributions at soft–hard interfaces and how they produce spatially heterogeneous properties in colloidal nanoparticles.

Monolayer transition metal dichalcogenides (TMDs) are promising for optoelectronics because of their high optical quantum yield and strong light-matter interaction. In particular, the van der Waals (vdW) heterostructures consisting of monolayer TMDs sandwiched by large gap hexagonal boron nitride have shown great potential for novel optoelectronic devices. However, a complicated stacking process limits scalability and practical applications. Furthermore, even though lots of efforts, such as fabrication of vdW heterointerfaces, modification of the surface, and structural phase transition, have been devoted to preserve or modulate the properties of TMDs, high environmental sensitivity and damage-prone characteristics of TMDs make it difficult to achieve a controllable technique for surface/interface engineering. Here, we demonstrate a novel way to fabricate multiple two-dimensional (2D) vdW heterostructures consisting of alternately stacked MoS2 and MoO x with enhanced photoluminescence (PL). We directly oxidized multilayer MoS2 to a MoO x /1 L-MoS2 heterostructure with atomic layer precision through a customized oxygen plasma system. The monolayer MoS2 covered by MoO x showed an enhanced PL intensity 3.2 and 6.5 times higher in average than the as-exfoliated 1 L- and 2 L-MoS2 because of preserved crystallinity and compensated dedoping by MoO x . By using layer-by-layer oxidation and transfer processes, we fabricated the heterostructures of MoO x /MoS2/MoO x /MoS2, where the MoS2 monolayers are separated by MoO x . The heterostructures showed the multiplied PL intensity as the number of embedded MoS2 layers increases because of suppression of the nonradiative trion formation and interlayer decoupling between stacked MoS2 layers. Our work shows a novel way toward the fabrication of 2D material-based multiple vdW heterostructures and our layer-by-layer oxidation process is beneficial for the fabrication of high performance 2D optoelectronic devices.

We introduce the "plasmonic nose" as a novel approach for detection, recognition, and quantification of mixtures of chemical species. Using a paper substrate and a calligraphy-based fabrication approach, we generated an array of surface-enhanced Raman scattering (SERS)-active sensors with distinct chemical functionalities. Each sensor is composed of gold nanorods (AuNRs) functionalized with a macromolecule that determined its sensitivity and specificity. We show that the SERS-active sensor array is capable of detecting and discriminating a wide variety of chemical species. To validate this approach, we exposed the sensor array to individual analytes and their binary/ternary mixtures. We found that each mixture generated a multivariate fingerprint that varied with identity (vibrational frequency) and intensity. Statistical analysis of SERS spectra from multiple sensors allowed us to not only recognize components of mixtures but also estimate their mixing ratios. In sum, our study presents a highly practical, low-cost sensing approach for quantitative chemical analyte detection for a wide variety of applications including life sciences, environmental monitoring, and homeland security.

Electromagnetic hotspots at the interstices of plasmonic assemblies are recognized to be the most potent sites for surface-enhanced Raman scattering (SERS). We demonstrate a novel "add-on" electromagnetic hotspot formation technique, which significantly improves the sensitivity of conventional SERS substrates composed of individual plasmonic nanostructures. The novel approach demonstrated here involves the transfer of "plasmonic patch", a transparent, flexible, and conformal elastomeric film adsorbed with plasmonic nanostructures, onto a conventional SERS substrate. The addition of the plasmonic patch onto a conventional SERS substrate following the analyte capture results in the formation of electromagnetic hotspots and hence a large SERS enhancement. The application of the plasmonic patch improves the sensitivity and limit of detection of conventional SERS substrates by up to ∼100-fold. The transfer of the plasmonic patch also effectively transforms the SERS-inactive gold mirror to a highly SERS-active "particle-on-mirror" system. Furthermore, we demonstrate that the "add-on" technique can be effectively utilized for the vapor-phase detection of explosives such as trinitrotoluene (TNT) using peptide recognition elements. We believe that the on-demand hotspot formation approach presented here represents a highly versatile and ubiquitously applicable technology readily expandable to any existing SERS substrate without employing complicated modification.

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