Plasmonic nanostructures possessing unique and versatile optoelectronic properties have been vastly investigated over the past decade. However, the full potential of plasmonic nanostructure has not yet been fully exploited, particularly with single-component homogeneous structures with monotonic properties, and the addition of new components for making multicomponent nanoparticles may lead to new-yet-unexpected or improved properties. Here we define the term “multi-component nanoparticles” as hybrid structures composed of two or more condensed nanoscale domains with distinctive material compositions, shapes, or sizes. We reviewed and discussed the designing principles and synthetic strategies to efficiently combine multiple components to form hybrid nanoparticles with a new or improved plasmonic functionality. In particular, it has been quite challenging to precisely synthesize widely diverse multicomponent plasmonic structures, limiting realization of the full potential of plasmonic heterostructures. To address this challenge, several synthetic approaches have been reported to form a variety of different multicomponent plasmonic nanoparticles, mainly based on heterogeneous nucleation, atomic replacements, adsorption on supports, and biomolecule-mediated assemblies. In addition, the unique and synergistic features of multicomponent plasmonic nanoparticles, such as combination of pristine material properties, finely tuned plasmon resonance and coupling, enhanced light-matter interactions, geometry-induced polarization, and plasmon-induced energy and charge transfer across the heterointerface, were reported. In this review, we comprehensively summarize the latest advances on state-of-art synthetic strategies, unique properties, and promising applications of multicomponent plasmonic nanoparticles. These plasmonic nanoparticles including heterostructured nanoparticles and composite nanostructures are prepared by direct synthesis and physical force- or biomolecule-mediated assembly, which hold tremendous potential for plasmon-mediated energy transfer, magnetic plasmonics, metamolecules, and nanobiotechnology.

The precise design and synthesis of plasmonic nanostructures allow us to manipulate, enhance, and utilize the optical characteristics of metallic materials. Although many multimeric structures (e.g., dimers) with interparticle nanogap have been heavily studied, the plasmonic nanostructures with a conductive junction have not been well studied mostly because of the lack of the reliable synthetic methods that can reproducibly and precisely generate a large number of the plasmonic nanostructures with a controllable conductive nanojunction. Here, we formed various asymmetric Au-Ag head-body nanosnowman structures with a highly controllable conductive nanojunction and studied their plasmon modes that cover from visible to near-infrared range, electromagnetic field enhancement, and surface-enhanced Raman scattering (SERS) properties. It was shown that change in the plasmonic neck region between Au head and Ag body nanoparticles and symmetry breaking using different sizes and compositions within a structure can readily and controllably introduce various plasmon modes and change the electromagnetic field inside and around a nanosnowman structure. The charge-transfer and capacitive coupling plasmon modes at low frequencies are tunable in the snowman structure, and subtle change in the conductive junction area of the nanosnowman dramatically affects the resulting electromagnetic field and optical signal. The relationships between the electromagnetic field distribution and enhancement in the snowman structure, excitation laser wavelength, and Raman dye were also studied, and it was found that the strongest electromagnetic field was observed in the crevice area on the junction and synthesizing a thinner and sharper neck junction is critical to generate the stronger electromagnetic field in the crevice area and to obtain the charge-transfer mode-based near-infrared signal. We have further shown that highly reproducible SERS signals can be generated from these nanosnowman structures with a linear dependence on particle concentration (5 fM to 1 pM) and the SERS-enhancement factor values of >10(8) can be obtained with the aid of the resonance effect in SERS. Finally, a wide range of LSPR bands with high tunability along with high structural reproducibility and high synthetic yield make the nanosnowman structures as very good candidates for practically useful multiple-wavelength-compatible, quantitative and sensitive SERS probes, and highly tunable nanoantenna structures.