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Strong couplings between molecular excitons and metal plasmons bring advantages to effectively manipulate the optical properties of hybrid systems, including both absorption and fluorescence. In contrast to absorption behaviours, which have been quite well understood and can be categorized into different regimes such as Fano dip and Rabi splitting, the characteristics of fluorescence in strongly coupled hybrids remain largely unexplored. Quenching instead of the enhancement of fluorescence is usually observed in the corresponding experiments, and a theoretical model to deal with this phenomenon is still lacking. Herein, we demonstrate a largely enhanced fluorescence in a hybrid system with Cy5 dye molecules strongly coupled to Ag nanoparticle films, signified by the huge Rabi splitting absorption spectra. The plexciton Rabi splitting of the hybrids can be tuned from 320 meV to as large as 750 meV by adjusting both plasmon strength and molecular concentration. Moreover, when the excitation and emission wavelengths are respectively tuned to be resonant with the two Rabi peaks, the hybrid acting as a plexcitonic dual resonant antenna exhibits an enhanced fluorescence 44 times larger than that of the free dye molecule. We also develop a theoretical model to simultaneously study the characteristics of both the absorption and emission spectra, including the peak shifting and strength. These findings offer a new strategy to design and fabricate plexcitonic devices with tunable optical responses and efficient fluorescence.

We synthesize Au@WS2 hybrid nanobelts and investigate their third-order nonlinear responses mediated by a strong anti-Stokes effect. By using the femtosecond Z-scan technique and tuning the excitation photon energy (Eexc), we find the sign reversals of both nonlinear absorption coefficient β and nonlinear refractive index γ to be around 1.60 eV, which is prominently higher than the bandgap (1.35 eV) of WS2 bulk owing to the strong anti-Stokes processes around the bandgap of the indirect semiconductors. The saturable absorption and self-defocusing of the WS2 nanobelts are significantly enhanced by the plasmon resonance of the Au nanoparticles when Eexc > 1.60 eV. But the excited state absorption assisted by the anti-Stokes processes and the self-focusing observed at Eexc < 1.60 eV are suppressed by the surface plasmon. Furthermore, by using population rate equations, we theoretically analyze the sign reversals of both β and γ and reveal the physical mechanism of the unique nonlinear responses of the hybrids with the plasmon resonance and anti-Stokes effect. These observations enrich the understanding of the nonlinear processes and interactions between the plasmon and exciton and are helpful for developing nonlinear optical nanodevices.

Plasmon-mediated energy transfer is highly desirable in photo-electronic nanodevices, but the direct injection efficiency of "hot electrons" in plasmonic photo-detectors and plasmon-sensitized solar cells (plasmon-SSCs) is poor. On another front, Fano resonance induced by strong plasmon-exciton coupling provides an efficient channel of coherent energy transfer from metallic plasmons to molecular excitons, and organic dye molecules have a much better injection efficiency in exciton-SSCs than "hot electrons". Here, we investigate enhanced light-harvesting of chlorophyll-a molecules strongly coupled to Au nanostructured films via Fano resonance. The enhanced local field and plasmon resonance energy transfer are experimentally revealed by monitoring the ultrafast dynamical processes of the plexcitons and the photocurrent flows of the assembled plexciton-SSCs. By tuning the Fano factor and anti-resonance wavelengths, we find that the local field is largely enhanced and the efficiency of plexciton-SSCs consisting of ultrathin TiO2 films is significantly improved. Most strikingly, the output power of the plexciton-SSCs is much larger than the sum of those of the individual plasmon- and exciton-SSCs. Our observations provide a practical approach to monitor energy and electron transfer in plasmon-exciton hybrids at a strong coupling regime and also offer a new strategy to design photovoltaic nanodevices.

This paper describes a facile method for the synthesis of Au/AuAg/Ag2S/PbS core-multishell nanorods with double trapping layers. The synthesis, in sequence, involved deposition of Ag shells onto the surfaces of Au nanorod seeds, formation of AuAg shells by a galvanic replacement reaction, and overgrowth of the Ag2S shells and PbS shells. The resulting core-multishell nanorod possesses an air gap between the Au core and the AuAg shell. Together with the Ag2S shell, the air gap can efficiently trap light, causing strong field confinement and nonlinear enhancement. The as-prepared Au/AuAg/Ag2S/PbS core-multishell nanorods display distinct localized surface plasmon resonance and nonlinear optical properties, demonstrating an effective pathway for maneuvering the optical properties of nanocavities.

We investigate tunable plasmon resonance and enhanced second harmonic generation (SHG) and up-converted fluorescence (UCF) of the hemispheric-like silver core/shell islands. The Ag, Ag/Ag2O, and Ag/Ag2O/Ag island films are prepared by using a sputtering technique. The SHG and UCF of the Ag/Ag2O/Ag core/shell islands near the percolating regime is enhanced 2.34 and 3.94 times compared to the sum of two individual counterparts of Ag/Ag2O core/shell and Ag shell islands. The ratio of SHG intensity induced by p- and s-polarization is 0.86 for the initial Ag islands and increase to 1.61 for the Ag/Ag2O/Ag core/shell samples. The tunable intensity ratio of SHG to UCF of the Ag islands treated by thermal and laser annealing processes is also observed. The physical mechanism of the enhanced SHG and UCF in the Ag/Ag2O/Ag core/shell islands is discussed. Our observations provide a new approach to fabricate plasmon-enhanced optical nonlinear nanodevices with tunable SHG and UCF.

Doping with intentional impurities is an intriguing way to tune the properties of semiconductor nanocrystals. However, the synthesis of some specific doped semiconductor nanocrystals remains a challenge and the doping mechanism in this strongly confined system is still not clearly understood. In this work, we report, for the first time, the synthesis of stable and water-soluble Ag-doped CdTe semiconductor quantum dots (SQDs) via a facile aqueous approach. Experimental characterization demonstrated the efficient doping of the Ag impurities into the CdTe SQDs with an appropriate reaction time. By doping 0.3% Ag impurities, the Stokes shift is decreased by 120 meV, the fluorescence intensity is enhanced more than 3 times, the radiative rate is enhanced 4.2 times, and the non-radiative rate is efficiently suppressed. These observations reveal that the fluorescence enhancement in Ag-doped CdTe SQDs is mainly attributed to the minimization of surface defects, filling of the trap states, and the enhancement of the radiative rate by the silver dopants. Our results suggest that the silver doping is an efficient method for tuning the optical properties of the CdTe SQDs.

Seeking plasmonic nanostructures with large field confinement and enhancement is significant for photonic and electronic nanodevices with high sensitivity, reproducibility, and tunability. Here, we report the synthesis of plasmonic arrays composed of two-segment dimer nanorods and coaxial cable nanorods with ∼1 nm gap insulated by a self-assembled Raman molecule monolayer. The gap-induced plasmon coupling generates an intense field in the gap region of the dimer junction and the cable interlayer. As a result, the longitudinal plasmon resonance of nanorod arrays with high tunability is obviously enhanced. Most interestingly, the field enhancement of dimer nanorod arrays can be tuned by the length ratio L1/L2 of the two segments, and the maximal enhancement appears at L1/L2 = 1. In that case, the two-photon luminescence (TPL) of dimer nanorod arrays and the Raman intensity in the dimer junction is enhanced by 27 and 30 times, respectively, under resonant excitation. In the same way, the Raman intensity in the gap region is enhanced 16 times for the coaxial cable nanorod arrays. The plasmonic nanorod arrays synthesized by the facile method, having tunable plasmon properties and large field enhancement, indicate an attractive pathway to the photonic nanodevices.

Upconversion materials have been employed as energy relay materials in dye sensitized solar cells (DSCs) to broaden the range of light absorption. However, the origin of the enhancements can be induced by both upconversion and size-dependent light scattering effects. To clarify the role of the upconversion material in the photoelectrode of DSCs, an upconversion induced device was realized here, which has the size-dependent light scattering effect eliminated via the application of NaYF4:Er(3+), Yb(3+)@SiO2 upconversion nanoparticles (β-NYEY@SiO2 UCNPs). An enhancement of 6% in efficiency was observed for the device. This demonstration provided an insight into the possible further employment of upconversion in DSCs.

We report the synthesis of 43-nm diameter Au nanocube dimers by using Ag(+) ions as competitive ligands to freeze L-cysteine-induced assembly process of the nanocubes to a desirable stage. Ascribed to the resonant interparticle coupling with an newly arising plasmon band at 710 nm and local field enhancement, the two-photon luminescence intensity of the Au nanocube dimers in solution was over 20 times stronger than that of the monomers in the wavelength range 555-620 nm. Furthermore, by coupling Raman tags onto the nanocube surface, a solution-based surface-enhanced Raman scattering (SERS) of the nanocube dimers had an enhancement factor of over 10 times compared to the isolated nanocubes. To sum up, with high stability in solution and attractive optical properties, the Au nanocube dimers have potential applications in in vivo bio-imaging and solution-based SERS.

The current challenge in catalyst development is to produce highly active and economical catalysts. This challenge cannot be overcome without an accurate understanding of catalyst structure, surfaces and morphology as the catalytic reactions occur on the surface active sites. Transmission Electron Microscopy (TEM) is an excellent tool for understanding the structures of the nanoparticles down to the atomic level in determining the relationship with the catalyst's performance in fuel cell applications. This paper describes a detailed structural characterization of Pt-Fe nanoparticles using aberration corrected TEM. Detailed analysis regarding the morphology, structural ordering, facets, nature of the surfaces, atomic displacements and compositions was carried out and presented in the context of their electrochemical performances. In addition, the effects of electrochemical cycling in terms of morphology and composition evolution of the nanoparticles were analyzed. Lastly, along with data from X-ray diffractometry, two different crystallographic models of the unknown Pt(3)Fe(2) nanoparticle phase are proposed. The detailed characterization by TEM provides useful insights into the nanoparticle chemistry and structure that contributes to catalyst development for next generation fuel cells.