TiN/anatase/rutile phase junction obtained by in-situ thermal transformation for efficient photothermal-assisted photocatalytic hydrogen generation.

Phase junctions exhibit great potential in photocatalytic energy conversion, yet the narrow light response region and inefficient charge transfer limit their photocatalytic performance. Herein, an anatase/rutile phase junction modified by plasmonic TiN and oxygen vacancies (TiN/(A-R-TiO2-Ov)) is prepared through an in-situ thermal transformation from TiN for efficient photothermal-assisted photocatalytic hydrogen production for the first time. The content of TiN, oxygen vacancies, and phase components in TiN/(A-R-TiO2-Ov) hybrids can be well-adjusted by tuning the heating time. The as-prepared photocatalysts display a large specific area and wide light absorption due to the synergistic effect of plasmonic excitation, oxygen vacancies, and bandgap excitations. Meanwhile, the multi-interfaces between TiN, anatase, and rutile provide built-in electric fields for efficient separation of photoinduced carriers and hot electron injection via ohmic contact and type-Ⅱ band arrangement. As a result, the TiN/(A-R-TiO2-Ov) photocatalyst shows an excellent photocatalytic hydrogen generation rate of 15.07 mmol/g/h, which is 20.6 times higher than that of titanium dioxide P25. Moreover, temperature-dependent photocatalytic tests reveal that the excellent photothermal conversion caused by plasmonic heating and crystal lattice vibrations in TiN/(A-R-TiO2-Ov) has about 25 % enhancement in photocatalysis (18.84 mmol/g/h). This work provides new inspiration for developing high-performance photocatalysts by optimizing charge transfer and photothermal conversion.

Open-Nanogap-Induced Strong Electromagnetic Enhancement in Au/AgAu Monolayer as a Stable and Uniform SERS Substrate for Ultrasensitive Detection.

Nanogap-based plasmonic metal nanocrystals have been applied in surface-enhanced Raman scattering detection, while the closed and insufficient electromagnetic fields as well as the nonreproducible Raman signal of the substrate greatly restrict the actual application. Herein, a highly uniform Au/AgAu monolayer with abundant nanogaps and huge electromagnetic enhancement is prepared, which shows ultrasensitive and reproducible SERS detection. Au/AgAu with an inner nanogap is first prepared based on Au nanotriangles, and the nanogap is opened from the three tips via a subsequent etching process. The open-gap Au/AgAu displays much higher SERS efficiency than Au and Au/AgAu with an inner nanogap on detecting crystal violet due to the open-gap induced electromagnetic enhancement and improved molecular absorption. Furthermore, the open-gap Au/AgAu monolayer is prepared via interfacial self-assembly, which shows further improved SERS due to the dense and strong hotspots in the nanocavities induced by the electromagnetic coupling between adjacent open gaps. The monolayer possesses excellent signal stability, uniformity, and reproducibility. The analytic enhancement factor and relative standard deviation reach to 2.12 × 108 and 4.65% on detecting crystal violet, respectively. Moreover, the monolayer achieves efficient detection of thiram in apple juice, biphenyl-4-thiol, 4-mercaptobenzoic, melamine, and a mixed solution of four different molecules, showing great promise in practical detection.

Plasmon-enhanced second harmonic generation of metal nanostructures.

As the most common nonlinear optical process, second harmonic generation (SHG) has important application value in the field of nanophotonics. With the rapid development of metal nanomaterial processing and chemical preparation technology, various structures based on metal nanoparticles have been used to achieve the enhancement and modulation of SHG. In the field of nonlinear optics, plasmonic metal nanostructures have become potential candidates for nonlinear optoelectronic devices because of their highly adjustable physical characteristics. In this article, first, the basic optical principles of SHG and the source of surface symmetry breaking in metal nanoparticles are briefly introduced. Next, the related reports on SHG in metal nanostructures are reviewed from three aspects: the enhancement of SHG efficiency by double resonance structures, the SHG effect based on magnetic resonance and the harmonic energy transfer. Then, the applications of SHG in the sensing, imaging and in situ monitoring of metal nanostructures are summarized. Future opportunities for SHG in composite systems composed of metal nanostructures and two-dimensional materials are also proposed.

Synergistic photothermal conversion and photocatalysis in 2D/2D MXene/Bi2S3 hybrids for efficient solar-driven water purification.

Plasmonic hybrids are regarded as promising candidates for water purification due to their structure-dependent photocatalysis and photothermal performance. It remains a challenge to develop materials that possess these two characteristics for efficient water purification. Herein, plasmonic Ti3C2Tx/Bi2S3 two-dimensional (2D)/2D hybrids were prepared for efficient solar-driven water purification via the combination of photothermal conversion and photocatalysis. Benefitting from broad light absorption, large 2D/2D interfaces, and efficient charge transfer, the binary hybrids showed high-efficiency photothermal conversion and photothermal-assisted photocatalytic activity. By depositing these 2D/2D hybrids on a hydrophilic and porous cotton piece, the Ti3C2Tx/Bi2S3 membrane displayed a high water evaporation rate and solar-to-vapor efficiency under one-sun irradiation. The solar-driven evaporation of seawater, heavy metal ion solution, and dye solution jointly indicated that the plasmonic membrane shows great potential for drinkable water generation and industrial wastewater treatment. Most importantly, the synergistic effect of photothermal evaporation and photocatalysis of the Ti3C2Tx/Bi2S3 membrane on water purification was demonstrated. The polluted water can not only be treated by evaporation, but also be degraded via photocatalysis under solar light irradiation. This work provides new insight into designing functional materials for water purification based on the combination of photothermal conversion and photocatalysis.

Optimized electromagnetic enhancement and charge transfer in MXene/Au/Cu2O hybrids for achieving efficient SERS.

The rational optimization of the electromagnetic field enhancement and charge transfer in a Raman substrate is vital for achieving efficient surface-enhanced Raman scattering (SERS). Herein, a ternary plasmonic substrate, whose structure-adjustable Au nanotriangle/Cu2O hybrids are combined with two-dimensional Ti3C2Tx MXene ultrathin nanosheets, is prepared and used for efficient SERS detection of molecules. By controlling the growth of Cu2O on Au nanotriangles, Au/Cu2O hybrids with three tips exposed are prepared, which show much better SERS performance than bare Au and core-shell Au@Cu2O in detecting methylene blue (MB) under excitation at 785 nm due to the optimized electromagnetic field enhancement and charge transfer. Furthermore, the Au/Cu2O hybrids are transferred to the plasmonic Ti3C2Tx nanosheet, generating a further enhanced electromagnetic field around their interfaces. As a result, the MXene/Au/Cu2O hybrids present further improved SERS activity, and their analytical enhancement factor reaches 2.4 × 109 and the detection limit is as low as 10-12 M. The enhancement mechanism can be ascribed to the improved electric field enhancement around the Au tips and the interface between MXene and Au/Cu2O. Meanwhile, the multiple charge-transfer processes between Au, Cu2O, MXene, and MB also play an important role in improving the SERS signal.

SPP standing waves within plasmonic nanocavities.

Surface plasmons usually take two forms: surface plasmon polaritons (SPP) and localized surface plasmons (LSP). Recent experiments demonstrate an interesting plasmon mode within plasmonic gaps, showing distinct characters from the two usual forms. In this investigation, by introducing a fundamental concept of SPP standing wave and an analytical model, we reveal the nature of the recently reported plasmon modes. The analytical model includes SPP propagating and SPP reflection within a metal-insulator-metal (MIM) cavity, which is rechecked and supplemented by numerical simulations. We systematically analyze SPP standing waves within various nanocavities. During the discussion, some unusual phenomena have been explained. For example, the hot spot of a nanodimer could be off-tip, depending on the order of standing wave mode; and that a nanocube on metal film can be viewed as a nanocube dimer with the same separation. And many other interesting phenomena have been discussed, such as dark mode of SPP standing wave and extraordinary optical transmission. The study gives a comprehensive understanding of SPP standing waves, and may promote the applications of cavity plasmons in ultrasensitive bio-sensings.

Ultrabroad spectral response and excellent SERS performance of PbS-assisted Au/PbS/Au nanostars.

Noble metal nanomaterials have many excellent optical properties due to localized surface plasmon resonance induced by external electric and magnetic fields. The plasmon-enhanced optical properties of nanomaterials can be controlled by changing their shapes or compositions. Here, we use a gentle approach to synthesize Au/PbS/Au nanostars with multiple tips and explore the surface-enhanced Raman scattering (SERS) activity, the second harmonic generation (SHG), and photocatalytic performance. The Au/PbS/Au nanostars have ultrabroad spectral responses and significantly enhanced local electric fields near the sharp tips. The size and tip length of the Au/PbS/Au nanostars can be adjusted by changing the amount of HAuCl4. The Au/PbS/Au nanostars exhibit largely enhanced SERS activity and photocatalytic degradation efficiency compared with the Au bipyramids and the Au BPs@PbS nanocrystals. In addition, the SHG of Au/PbS/Au nanostars is also significantly enhanced due to asymmetry and local field enhancement. This research shows potential in many applications ranging from photophysics to photochemistry.

Toroidal dipole-modulated dipole-dipole double-resonance in colloidal gold rod-cup nanocrystals for improved SERS and second-harmonic generation.

Colloidal metal nanocrystals (NCs) show great potential in plasmon-enhanced spectroscopy owing to their attractive and structure-depended plasmonic properties. Herein, unique Au rod-cup NCs, where Au nanocups are embedded on the one or two ends of Au nanorods (NRs), are successfully prepared for the first time via a controllable wet-chemistry strategy. The Au rod-cup NCs possess multiple plasmon modes including transverse and longitudinal electric dipole (TED and LED), magnetic dipole (MD), and toroidal dipole (TD) modulated LED resonances, producing large extinction cross-section and huge near-field enhancements for plasmon-enhanced spectroscopy. Particularly, Au rod-cup NCs with two embedded cups show excellent surface-enhanced Raman spectroscopy (SERS) performance than Au NRs (75.6-fold enhancement excited at 633 nm) on detecting crystal violet owing to the strong electromagnetic hotspots synergistically induced by MD, LED, and TED-based plasmon coupling between Au cup and rod. Moreover, the strong TD-modulated dipole-dipole double-resonance and MD modes in Au rod-cup NCs bring a 37.3-fold enhancement of second-harmonic generation intensity compared with bare Au NRs, because they can efficiently harvest photoenergy at fundamental frequency and generate large near-field enhancements at second-harmonic wavelength. These findings provide a strategy for designing optical nanoantennas for plasmon-enhanced applications based on multiple plasmon modes. Electronic Supplementary Material: Supplementary material (SEM image of Au rod-one-cup NCs; TEM image of Au/PbS hybrids; SEM image of Au rod-two-cup NCs; low-amplification SEM image of Au rod-two-cup NCs; experimental extinction and calculated electric field distributions of Au NR excited at different wavelengths; calculated absorption and scattering spectra of Au rod-one-cup NCs; schematic illustration of the cut plane and the corresponding magnetic field distribution under L3 excitation; Raman spectra of CV (10-6 M) adsorbed on Au rod-cup NCs with different cup sizes; calculated magnetic field distribution of Au rodcup NCs excited at 532 and 633 nm; calculated electric field distributions of Au rod-one-cup NC excited at 600 nm along TE and LE; the models of Au rod-cup NCs used in the simulations) is available in the online version of this article at 10.1007/s12274-022-4562-5.

Plasmon Coupling and Efficient Charge Transfer in Rough-Surfaced Au Nanotriangles/MXene Hybrids as an Ultrasensitive Surface-Enhanced Raman Scattering Platform.

The rational design of Raman substrate materials with prominent electromagnetic enhancement and charge transfer is quite important for surface-enhanced Raman scattering (SERS). Herein, an efficient SERS substrate based on two-dimensional ultrathin Ti3C2T x MXene and rough-surfaced Au nanotriangles (NTs) was successfully prepared for efficient detection of organic molecules due to the synthetic effect of an optimized electromagnetic field and charge transfer. Uniform Au NTs with tunable surface roughness were controllably prepared by selectively depositing of Au on the smooth Au NTs. Due to the large surface area, tunable plasmon resonance, and abundant hotspots on the planar surface, the modified Au NTs showed much better SERS performance than initial Au NTs. By combination of the rough-surfaced Au NTs with MXene, the Ti3C2T x /Au NT hybrids exhibited much better SERS performance than initial Au NTs and Au NTs with a rough surface. The detection limit is down to 10-12 M, and the analytical enhancement factors reach 3.6 × 109 (at 1174 cm-1) on detecting crystal violet excited at 785 nm. This is because the strong plasmon coupling between the in-plane resonance of Au NTs and transversal plasmon resonance of Ti3C2T x MXene around 785 nm can generate an intense interfacial electromagnetic field for amplifying SERS signals. Additionally, the efficient charge transfer between Au NTs, MXene, and molecules also plays an important role in enhancing the SERS performance. This work presents a new insight to develop high-performance SERS substrates based on plasmon.

Synthesis of AuAg/Ag/Au open nanoshells with optimized magnetic plasmon resonance and broken symmetry for enhancing second-harmonic generation.

The cooperation of magnetic and electric plasmon resonances in cup-shaped metallic nanostructures exhibits significant capability for second-harmonic generation (SHG) enhancement. Herein, we report an approach for synthesizing Au open nanoshells with tunable numbers and sizes of openings on a template of six-pointed PbS nanostars. The morphology of Au nanoshells is controlled by adjusting the amount of HAuCl4, and the characteristic shapes of pointed nanocaps, open nanoshells, and hollow nanostars are obtained. Owing to the collaboration of electric and magnetic plasmon resonance modes, the Au nanoshells exhibit significantly broadened and highly tunable optical responses. Furthermore, the morphology-dependent SHG of the Au nanoshells shows two maximal SHG intensities, corresponding to four-opening and one-opening Au nanoshells with appropriate opening sizes. Ag/Au and AuAg/Ag/Au open nanoshells were further investigated to achieve enhanced SHG. By adjusting the thickness of the Ag shell, the SHG intensity of Ag/Au open nanoshells reaches a maximum due to the gradient field at the AuAg bimetallic interface. After replacing the Ag shells with Au shells, the SHG intensity of AuAg/Ag/Au open nanoshells reaches a maximum due to further symmetry breaking. These findings provide a strategy to prepare colloidal metal nanocrystals with prospective applications ranging from nonlinear photonic nanodevices to biospectroscopy and photocatalysis.

Strong Visible Light Absorption and Abundant Hotspots in Au-Decorated WO3 Nanobricks for Efficient SERS and Photocatalysis.

Metal/semiconductor hybrids show potential application in fields of surface-enhanced Raman spectroscopy (SERS) and photocatalysis due to their excellent light absorption, electric field, and charge-transfer properties. Herein, a WO3-Au metal/semiconductor hybrid, which was a WO3 nanobrick decorated with Au nanoparticles, was prepared via a facile hydrothermal method. The WO3-Au hybrids show excellent visible light absorption, strong plasmon coupling, high-performance SERS, and good photocatalytic activity. In particular, on sensing rhodamine B (RhB) under 532 nm excitation, bare WO3 nanobricks have a Raman enhancement factor of 2.0 × 106 and a limit of detection of 10-8 M due to the charger-transfer property and abundant oxygen vacancies. WO3-Au metal/semiconductor hybrids display a largely improved Raman enhancement factor compared to pure Au and WO3 components owing to the synergistic effect of electromagnetic enhancement and charge transfer. The Raman enhancement factor and limit of detection are further improved, reaching 5.3 × 108 and 10-12 M, respectively, on increasing the content of Au to 2.1 wt %, owing to the strong plasmon coupling between the Au nanoparticles. Additionally, the WO3-Au hybrids also exhibit excellent photocatalytic activity toward degradation of RhB under visible light irradiation. WO3-Au (2.1 wt %) possesses the fastest photocatalytic rate, which is 6.1 and 2.0 times that of pure WO3 nanobricks and commercial P25, respectively. The enhanced photocatalytic activity is attributed to the strong plasmon coupling and the efficient charge transfer between Au and WO3 nanobricks. The as-prepared materials show great potential in detecting and degrading pollutants in environmental treatment.

Dual Plasmon Resonances and Tunable Electric Field in Structure-Adjustable Au Nanoflowers for Improved SERS and Photocatalysis.

Flower-like metallic nanocrystals have shown great potential in the fields of nanophononics and energy conversion owing to their unique optical properties and particular structures. Herein, colloid Au nanoflowers with different numbers of petals were prepared by a steerable template process. The structure-adjustable Au nanoflowers possessed double plasmon resonances, tunable electric fields, and greatly enhanced SERS and photocatalytic activity. In the extinction spectra, Au nanoflowers had a strong electric dipole resonance located around 530 to 550 nm. Meanwhile, a longitudinal plasmon resonance (730~760 nm) was obtained when the number of petals of Au nanoflowers increased to two or more. Numerical simulations verified that the strong electric fields of Au nanoflowers were located at the interface between the Au nanosphere and Au nanopetals, caused by the strong plasmon coupling. They could be further tuned by adding more Au nanopetals. Meanwhile, much stronger electric fields of Au nanoflowers with two or more petals were identified under longitudinal plasmon excitation. With these characteristics, Au nanoflowers showed excellent SERS and photocatalytic performances, which were highly dependent on the number of petals. Four-petal Au nanoflowers possessed the highest SERS activity on detecting Rhodamine B (excited both at 532 and 785 nm) and the strongest photocatalytic activity toward photodegrading methylene blue under visible light irradiation, caused by the strong multi-interfacial plasmon coupling and longitudinal plasmon resonance.

Plasmon-Mediated 2D/2D Phase Junction for Improved Photocatalytic Hydrogen Generation Activity.

A phase junction fabricated by two crystalline phases of the same semiconductor is a promising photocatalyst with efficient charge transfer and separation. However, the weak light absorption and uncontrolled phase junction interface limit the generation and separation of photogenerated carriers. Herein, a two-dimensional (2D)/2D phase junction was prepared by growing orthorhombic WO3 ultrathin nanosheets on hexagonal WO3 nanosheets through a one-step hydrothermal method. The orthorhombic/hexagonal WO3 possesses large-area phase junction interfaces, rich reactive sites, and built-in electric field, which greatly accelerate the photogenerated charge separation and transfer. Thus, the orthorhombic/hexagonal WO3 displayed excellent photocatalytic hydrogen generation activity from water splitting under light irradiation (λ > 420 nm), which is 2.16 and 2.85 times those of orthorhombic and hexagonal WO3 phase components. Furthermore, Au nanoparticles (about 4.5 nm in diameter) were deposited on both orthorhombic and hexagonal WO3 nanosheets to form a plasmon-mediated phase junction. The hybrids exhibit prominent visible-light absorption and efficient charge transfer, leading to a further improved photocatalytic hydrogen generation activity. Further characterization studies demonstrate that superior photoactivity arises from the excellent visible-light-harvesting ability, appropriate band structure, and high-efficiency and multichannel transferring processes of photogenerated carriers.

Tunable Size Dependence of Quantum Plasmon of Charged Gold Nanoparticles.

The quantum behavior of surface plasmons has received extensive attention, benefiting from the development of exquisite nanotechnology and the diverse applications. Blueshift, redshift, and nonshift of localized surface plasmon resonances (LSPRs) have all been reported as the particle size decreases and enters the quantum size regime, but the underlying physical mechanism to induce these controversial size dependences is not clear. Herein, we propose an improved semiclassical model for modifying the dielectric function of metal nanospheres by combining the intrinsic quantized electron transitions and surface electron injection or extraction to investigate the plasmon shift and LSPR size dependence of the charged Au nanoparticles. We experimentally observe that the nonmonotonic blueshift of LSPRs with size for Au nanoparticles is turned into an approximately monotonic blueshift by increasing the electron donor concentration in the reduction solution, and it can also be transformed to an approximately monotonic redshift after surface passivation by ligand molecules. Moreover, we demonstrate controlled blueshift and redshift for the electron and hole plasmons in Cu_{2-x}S@Au core-shell nanoparticles by injecting electrons. The experimental observations and the theoretical calculations clarify the controversial size dependences of LSPR reported in the literature, reveal the critical role of surface electron injection or extraction in the transformation between the different size dependences of LSPRs, and are helpful for understanding the nature of surface plasmons in the quantum size regime.

Growth of Porous Ag@AuCu Trimetal Nanoplates Assisted by Self-Assembly.

The self-assembly process of metal nanoparticles has aroused wide attention due to its low cost and simplicity. However, most of the recently reported self-assembly systems only involve two or fewer metals. Herein, we first report a successful synthesis of self-assembled Ag@AuCu trimetal nanoplates in aqueous solution. The building blocks of multibranched AuCu alloy nanocrystals were first synthesized by a chemical reduction method. The growth of Ag onto the AuCu nanocrystals in the presence of hexadecyltrimethylammonium chloride (CTAC) induces a self-assembly process and formation of Ag@AuCu trimetal nanoplates. These nanoplates with an average side length of over 2 µm show a porous morphology and a very clear boundary with the branches of the as-prepared AuCu alloy nanocrystals extending out. The shape and density of the Ag@AuCu trimetal nanoplates can be controlled by changing the reaction time and the concentration of silver nitrate. The as-assembled Ag@AuCu nanoplates are expected to have the potential for wide-ranging applications in surface-enhanced Raman scattering (SERS) and catalysis owing to their unique structures.

Structure-Adjustable Gold Nanoingots with Strong Plasmon Coupling and Magnetic Resonance for Improved Photocatalytic Activity and SERS.

Au nanoingots, on which an Au nanosphere is accurately placed in an open Au shell, are synthesized through a controllable hydrothermal method. The prepared Au nanoingots exhibit an adjustable cavity structure, strong plasmon coupling, tunable magnetic plasmon resonance, and prominent photocatalytic and SERS performances. Au nanoingots exhibit two resonance peaks in the extinction spectrum, one (around 550 nm) is ascribed to electric dipole resonance coming from the central Au, and the other one (650-800 nm) is ascribed to the magnetic dipole resonance originating from the open Au shell. Numerical simulations verify that the intense electric and magnetic fields locate in the bowl-shaped nanogap between the Au nanosphere and shell, and they can be further optimized by changing the size of the outer Au shell. Au nanoingots with the largest shell have the strongest electric field because of large-area plasmon coupling, while Au nanoingots with the largest shell opening size have the strongest magnetic field. As a result, the structure-adjustable Au nanoingots show a high tunability and enhancement of catalytic reduction of p-nitrophenol and SERS detection of Rhodamine B. Specially, Au nanoingots with the largest shell size exhibit the highest catalytic activity and Raman signals at 532 nm excitation. However, Au nanoingots with the largest shell opening size have the highest photocatalytic activity with light irradiation (λ > 420 nm) and exhibit the best SERS performance at 785 nm excitation.

Multi-interfacial plasmon coupling in multigap (Au/AgAu)@CdS core-shell hybrids for efficient photocatalytic hydrogen generation.

Plasmon coupling induced intense light absorption and near-field enhancement have vast potential for high-efficiency photocatalytic applications. Herein, (Au/AgAu)@CdS core-shell hybrids with strong multi-interfacial plasmon coupling were prepared through a convenient strategy for efficient photocatalytic hydrogen generation. Bimetallic Au/AgAu cores with an adjustable number of nanogaps (from one to four) were primarily synthesized by well-controlled multi-cycle galvanic replacement and overgrowth processes. Extinction tests and numerical simulations synergistically revealed that the multigap Au/AgAu hybrids possess a gap-dependent light absorption region and a local electric field owing to the multigap-induced multi-interfacial plasmon coupling. With these characteristics, hetero-photocatalysts prepared by further coating of CdS shells on multigap Au/AgAu cores exhibited a prominent gap-dependent photocatalytic hydrogen production activity from water splitting under light irradiation (λ > 420 nm). It is found that the hydrogen generation rates of multigap (Au/AgAu)@CdS have an exponential improvement compared with that of pure CdS as the number of nanogaps increases. In particular, four-gap (Au/AgAu)@CdS core-shell catalysts displayed the highest hydrogen generation rate, that is 96.1 and 47.2 times those of pure CdS and gapless Au@CdS core-shell hybrids. These improvements can be ascribed to the strong plasmon absorption and near-field enhancement induced by the multi-interfacial plasmon coupling, which can greatly improve the light-harvesting efficiency, offer more plasmonic energy, and boost the generation and separation of electron-hole pairs in the multigap catalysts.

Asymmetric synthesis of Au-CdSe core-semishell nanorods for plasmon-enhanced visible-light-driven hydrogen evolution.

The metal-semiconductor heterostructure is an important candidate for photocatalysis due to its efficient charge transport and separation. A controllable morphology and ideal interfaces are critically significant for improving the heterostructure photocatalytic performance. By controlling the concentration of Cd2+ to control the reaction environment (pH value) and reaction rate, the CdSe nanocrystal is overgrown on the side or tip of the Au nanorods, which leads to a strong interaction between the excitons of CdSe nanocrystals and the plasmons of Au nanorods. Both kinds of Au-CdSe heterorods exhibit good hydrogen productivity. Particularly, the lateral Au-CdSe heterorods exhibit excellent photocatalytic efficiency due to the larger contact interface of Au and CdSe and the strong local field of the CdSe nanocrystals grown on one side of the Au nanorods being enhanced by the transverse plasmon resonance in the visible region. We provide an approach to modulate the combination of the asymmetric metal nanoparticle and the semiconductor shell; these core-semishell heterostructures have potential applications ranging from photocatalysis to photonic nanodevices.

Growth of Au Hollow Stars and Harmonic Excitation Energy Transfer.

Optical excitation, subsequent energy transfer, and emission are fundamental to many physical problems. Optical antennas are ideal candidates for manipulating these processes. We extend energy transfer to second- and third-harmonic (SH and TH) fields through the collaborative susceptibility χ(n) (n = 1, 2, 3) resonances of nonlinear optical antennas. Hollow gold stars, with a broadband response covering the fundamental, SH, and TH frequencies, are synthesized as nonlinear antennas. Harmonic resonance energy transfer through a χ(3) → χ(1) collaboration is revealed. A χ(3) → χ(2) collaboration is uncovered, with largely enhanced SH radiation demonstrated by exciting the three resonances at the fundamental, SH, and TH frequencies. A theoretical model of the effective nonlinear susceptibilities is proposed to calculate the efficiencies of the two nonlinear energy transfer processes.

Manipulating the fluorescence of exciton-plasmon hybrids in the strong coupling regime with dual resonance enhancements.

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.