Hot electron chemistry has drawn tremendous attention from applications related to materials, energy, sensing, and catalysis. The plasmon‐induced generation of hot electrons and their transfer behavior are very important for understanding plasmonic‐enhanced applications and for achieving practically useful efficiency. From a plasmonic perspective, well‐designed plasmonic structures that can manipulate surface plasmons are able to enhance the efficiencies of hot electron‐based processes. This progress report summarizes the recent experimental and theoretical advances on the hot electron effect, emphasizing the crucial role of surface plasmons that are highly designable by using metal nanostructures. In particular, recent breakthroughs in the emerging fields of heterogeneous catalysis based on the hot electron effect are highlighted. Important design principles, mechanisms, and concepts, as well as challenges and perspectives, are illustrated and discussed.
Uniformly controlling a large number of metal nanostructures with a plasmonically enhanced signal to generate quantitative optical signals and the widespread use of these structures for surface-enhanced Raman scattering (SERS)-based biosensing and bioimaging applications are of paramount importance but are extremely challenging. Here, we report a highly controllable, facile selective-interdiffusive dealloying chemistry for synthesizing the dealloyed intra-nanogap particles (DIPs) with a ∼2 nm intragap in a high yield (∼95%) without the need for an interlayer. The SERS signals from DIPs are highly quantitative and polarization-independent with polarized laser sources. Remarkably, all the analyzed particles displayed the SERS enhancement factors (EFs) of ≥1.1 × 108 with a very narrow distribution of EFs. Finally, we show that DIPs can be used as ultrasensitive SERS-based DNA detection probes for detecting 10 aM to 1 pM target concentrations and highly robust, quantitative real-time cell imaging probes for long-term imaging with low laser power and short exposure time.
Herein, we report the novel strategy for the synthesis of complex 3-dimensional (3D) nanostructures, mimicking the linker molecule-free 3D arrangement of six Au nanospheres at the vertices of octahedrons. We utilized 3D PtAu skeleton for the structural rigidity and deposited Au around the PtAu skeleton in a site-selective manner, allowing us to investigate their surface plasmonic coupling phenomenon and near-field enhancement as a function of sizes of nanospheres, which are directly related to the intrananogap distance and interior volume size. The resulting 3D Au hexamer structures with octahedral arrangement were realized through precise control of the Au growth pattern. The complex 3D Au hexamers were composed of six Au nanospheres connected by thin metal conductive bridges. The standard deviation of the metal conductive bridges and Au nanospheres was within ca. 10%, exhibiting a high degree of homogeneity and precise structural tunability. Interestingly, charge transfer among the six Au nanospheres occurred along the metal conductive bridges leading to surface plasmonic coupling between Au nanospheres. Accordingly, electric near fields were strongly and effectively focused at the vertices, intrananogap regions between Au nanospheres, and interior space, exhibiting well-resolved single-particle surface-enhanced Raman spectroscopy signals of absorbed analytes.
The plasmonic properties of metal nanostructures have been heavily utilized for surface-enhanced Raman scattering (SERS) and metal-enhanced fluorescence (MEF), but the direct photoluminescence (PL) from plasmonic metal nanostructures, especially with plasmonic coupling, has not been widely used as much as SERS and MEF due to the lack of understanding of the PL mechanism, relatively weak signals, and the poor availability of the synthetic methods for the nanostructures with strong PL signals. The direct PL from metal nanostructures is beneficial if these issues can be addressed because it does not exhibit photoblinking or photobleaching, does not require dye-labeling, and can be employed as a highly reliable optical signal that directly depends on nanostructure morphology. Herein, we designed and synthesized plasmonic cube-in-cube (CiC) nanoparticles (NPs) with a controllable interior nanogap in a high yield from Au nanocubes (AuNCs). In synthesizing the CiC NPs, we developed a galvanic void formation (GVF) process, composed of replacement/reduction and void formation steps. We unraveled the super-radiant character of the plasmonic coupling-induced plasmon mode which can result in highly enhanced PL intensity and long-lasting PL, and the PL mechanisms of these structures were analyzed and matched with the plasmon hybridization model. Importantly, the PL intensity and quantum yield (QY) of CiC NPs are 31 times and 16 times higher than those of AuNCs, respectively, which have shown the highest PL intensity and QY reported for metallic nanostructures. Finally, we confirmed the long-term photostability of the PL signal, and the signal remained stable for at least 1 h under continuous illumination.
Surface-enhanced Raman scattering (SERS) provides significantly enhanced Raman scattering signals from molecules adsorbed on plasmonic nanostructures, as well as the molecules' vibrational fingerprints. Plasmonic nanoparticle systems are particularly powerful for SERS substrates as they provide a wide range of structural features and plasmonic couplings to boost the enhancement, often up to >10 8 −10 10 . Nevertheless, nanoparticle-based SERS is not widely utilized as a means for reliable quantitative measurement of molecules largely due to limited controllability, uniformity, and scalability of plasmonic nanoparticles, poor molecular modification chemistry, and a lack of widely used analytical protocols for SERS. Furthermore, multiscale issues with plasmonic nanoparticle systems that range from atomic and molecular scales to assembled nanostructure scale are difficult to simultaneously control, analyze, and address. In this perspective, we introduce and discuss the design principles and key issues in preparing SERS nanoparticle substrates and the recent studies on the uniform and controllable synthesis and newly emerging machine learning-based analysis of plasmonic nanoparticle systems for quantitative SERS. Specifically, the multiscale point of view with plasmonic nanoparticle systems toward quantitative SERS is provided throughout this perspective. Furthermore, issues with correctly estimating and comparing SERS enhancement factors are discussed, and newly emerging statistical and artificial intelligence approaches for analyzing complex SERS systems are introduced and scrutinized to address challenges that cannot be fully resolved through synthetic improvements.
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