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1.
Novel CdSe quantum dot (QD)-sensitized Au/TiO2 hybrid mesoporous films have been designed, fabricated, and evaluated for photoelectrochemical (PEC) applications. The Au/TiO2 hybrid structures were made by assembly of Au and TiO2 nanoparticles (NPs). A chemical bath deposition method was applied to deposit CdSe QDs on TiO2 NP films with and without Au NPs embedded. We observed significant enhancements in photocurrent for the film with Au NPs, in the entire spectral region we studied (350–600 nm). Incident-photon-to-current efficiency (IPCE) data revealed an average enhancement of 50%, and the enhancement was more significant at short wavelength. This substantially improved PEC performance is tentatively attributed to the increased light absorption of CdSe QDs due to light scattering by Au NPs. Interestingly, without QD sensitization, the Au NPs quenched the photocurrent of TiO2 films, due to the dominance of electron trapping over light scattering by Au NPs. The results suggest that metal NPs are potentially useful for improving the photoresponse in PEC cells and possibly in other devices such as solar cells based on QD-sensitized metal oxide nanostructured films. This work demonstrates that metal NPs can serve as light scattering centers, besides functioning as photo-sensitizers and electron traps. The function of metal NPs in a particular nanocomposite film is strongly dependent on their structure and morphology.   相似文献   

2.
A hierarchically patterned metal/semiconductor (gold nanoparticles/ZnO nanowires) nanostructure with maximized photon trapping effects is fabricated via interference lithography (IL) for plasmon enhanced photo‐electrochemical water splitting in the visible region of light. Compared with unpatterned (plain) gold nanoparticles‐coated ZnO NWs (Au NPs/ZnO NWs), the hierarchically patterned Au NPs/ZnO NWs hybrid structures demonstrate higher and wider absorption bands of light leading to increased surface enhanced Raman scattering due to the light trapping effects achieved by the combination of two different nanostructure dimensions; furthermore, pronounced plasmonic enhancement of water splitting is verified in the hierarchically patterned Au NPs/ZnO NWs structures in the visible region. The excellent performance of the hierarchically patterned Au NPs/ZnO NWs indicates that the combination of pre‐determined two different dimensions has great potential for application in solar energy conversion, light emitting diodes, as well as SERS substrates and photoelectrodes for water splitting.  相似文献   

3.
The performance of plasmonic Au nanostructure/metal oxide heterointerface shows great promise in enhancing photoactivity, due to its ability to confine light to the small volume inside the semiconductor and modify the interfacial electronic band structure. While the shape control of Au nanoparticles (NPs) is crucial for moderate bandgap semiconductors, because plasmonic resonance by interband excitations overlaps above the absorption edge of semiconductors, its critical role in water splitting is still not fully understood. Here, first, the plasmonic effects of shape‐controlled Au NPs on bismuth vanadate (BiVO4) are studied, and a largely enhanced photoactivity of BiVO4 is reported by introducing the octahedral Au NPs. The octahedral Au NP/BiVO4 achieves 2.4 mA cm?2 at the 1.23 V versus reversible hydrogen electrode, which is the threefold enhancement compared to BiVO4. It is the highest value among the previously reported plasmonic Au NPs/BiVO4. Improved photoactivity is attributed to the localized surface plasmon resonance; direct electron transfer (DET), plasmonic resonant energy transfer (PRET). The PRET can be stressed over DET when considering the moderate bandgap semiconductor. Enhanced water oxidation induced by the shape‐controlled Au NPs is applicable to moderate semiconductors, and shows a systematic study to explore new efficient plasmonic solar water splitting cells.  相似文献   

4.
MoS2 shows promising applications in photocatalytic water splitting, owing to its uniquely optical and electric properties. However, the insufficient light absorption and lack of performance stability are two crucial issues for efficient application of MoS2 nanomaterials. Here, Au nanoparticles (NPs)@MoS2 sub‐micrometer sphere‐ZnO nanorod (Au NPs@MoS2‐ZnO) hybrid photocatalysts have been successfully synthesized by a facile process combining the hydrothermal method and seed‐growth method. Such photocatalysts exhibit high efficiency and excellent stability for hydrogen production via multiple optical‐electrical effects. The introduction of Au NPs to MoS2 sub‐micrometer spheres forming a core–shell structure demonstrates strong plasmonic absorption enhancement and facilitates exciton separation. The incorporation of ZnO nanorods to the Au NPs@MoS2 hybrids further extends the light absorption to a broader wavelength region and enhances the exciton dissociation. In addition, mutual contacts between Au NPs (or ZnO nanorods) and the MoS2 spheres effectively protect the MoS2 nanosheets from peeling off from the spheres. More importantly, efficiently multiple exciton separations help to restrain the MoS2 nanomaterials from photocorrosion. As a result, the Au@MoS2‐ZnO hybrid structures exhibit an excellent hydrogen gas evolution (3737.4 μmol g?1) with improved stability (91.9% of activity remaining) after a long‐time test (32 h), which is one of the highest photocatalytic activities to date among the MoS2 based photocatalysts.  相似文献   

5.
Engineering a facile and controllable approach to modulate the spectral properties of lanthanide‐doped upconversion nanoparticles (UCNPs) is always an ongoing challenge. Herein, long‐range ordered, distinct two‐dimensional (2D) binary nanoparticle superlattices (BNSLs) composed of NaREF4:Yb/Er (RE = Y and Gd) UCNPs and plasmonic metallic nanoparticles (Au NPs), including AB, AB3, and AB13 lattices, are fabricated via a slow evaporation‐driven self‐assembly to achieve plasmonic modulation of upconversion luminescence (UCL). Optical measurements reveal that typical red–green UCL from UCNPs can be effectively modulated into reddish output in BNSLs, with a drastically shortened lifetime. Notably, for AB3‐ and AB13‐type BNSLs with more proximal Au NPs around each UCNP, modified UCL with fine‐structured spectral lineshape is observed. These differences could be interpreted by the interplay of collective plasmon resonance introduced by 2D periodic Au arrays and spectrally selective energy transfer between UCNPs and Au. Thus, fabricating UCNP‐Au BNSLs with desired lattice parameters and NP configurations could be a promising way to tailor the UCL through controlled plasmonic modulation.  相似文献   

6.
In recent years, optical chirality of plasmonic nanostructures has aroused great interest because of innovative fundamental understanding as well as promising potential applications in optics, catalysis and sensing. Herein, state‐of‐the‐art studies on circular dichroism (CD) characteristics of plasmonic nanostructures are summarized. The hybrid of achiral plasmonic nanoparticles (NPs) and chiral molecules is explored to generate a new CD response at the plasmon resonance as well as the enhanced CD intensity of chiral molecules in the UV region, owing to the Coulomb static and dynamic dipole interactions between plasmonic NPs and chiral molecules. As for chiral assembly of plasmonic NPs, plasmon–plasmon interactions between the building blocks are found to induce generation of intense CD response at the plasmon resonance. Three‐dimensional periodical arrangement of plasmonic NPs into macroscale chiral metamaterials is further introduced from the perspective of negative refraction and photonic bandgap. A strong CD signal is also discerned in achiral planar plasmonic nanostructures under illumination of circular polarized plane wave at oblique incidence or input vortex beam at normal incidence. Finally perspectives, especially on future investigation of time‐resolved CD responses, are presented.  相似文献   

7.
A highly sensitive avalanche photodetector (APD) is fabricated by utilizing the avalanche multiplication mechanism in black phosphorus (BP), where a strong avalanche multiplication of electron–hole pairs is observed. Owing to the small bandgap (0.33 eV) of the multilayer BP, the carrier multiplication occurs at a significantly lower electric field than those of other 2D semiconductor materials. In order to further enhance the quantum efficiency and increase the signal‐to‐noise (S/N) ratio, Au nanoparticles (NPs) are integrated on the BP surface, which improves the light absorption by plasmonic effects. The BP–Au‐NPs structure effectively reduces both dark current (≈10 times lower) and onset of avalanche electric field, leading to higher carrier multiplication, photogain, quantum efficiency, and S/N ratio. For the BP–Au‐NPs APD, it is obtained that the external quantum efficiency (EQE) is 382 and the responsivity is 160 A W‐1 at an electric field of 5 kV cm‐1 (Vd ≈ 3.5 V, note that for the BP APD, EQE = 4.77 and responsivity = 2 A W‐1 obtained at the same electric field). The significantly increased performance of the BP APD is promising for low‐power‐consumption, high‐sensitivity, and low‐noise photodevice applications, which can enable high‐performance optical communication and imaging systems.  相似文献   

8.
The exploitation of photocatalysts that harvest solar spectrum as broad as possible remains a high‐priority target yet grand challenge. In this work, for the first time, metal–organic framework (MOF) composites are rationally fabricated to achieve broadband spectral response from UV to near‐infrared (NIR) region. In the core–shell structured upconversion nanoparticles (UCNPs)‐Pt@MOF/Au composites, the MOF is responsive to UV and a bit visible light, the plasmonic Au nanoparticles (NPs) accept visible light, whereas the UCNPs absorb NIR light to emit UV and visible light that are harvested by the MOF and Au once again. Moreover, the MOF not only facilitates the generation of “bare and clean” Au NPs on its surface and realizes the spatial separation for the Au and Pt NPs, but also provides necessary access for catalytic substrates/products to Pt active sites. As a result, the optimized composite exhibits excellent photocatalytic hydrogen production activity (280 µmol g?1 h?1) under simulated solar light, and the involved mechanism of photocatalytic H2 production under UV, visible, and NIR irradiation is elucidated. Reportedly, this is an extremely rare study on photocatalytic H2 production by light harvesting in all UV, visible, and NIR regions.  相似文献   

9.
Magnetic–plasmonic hybrid nanoparticles (MPHNs) have attracted great interest in cancer theranostics. However, the relaxivity of the magnetic component is typically reduced by the plasmonic component in conventional core–shell structured MPHNs, due to the presence of a water‐impenetrable coating which severely restricts the proximity of protons to the magnetic portion. To circumvent this issue, yolk–shell structured MPHNs comprising a Fe3O4 core within a hollow cavity encircled by a porous Au outer shell are designed. As expected, the introduction of hollow cavity between the magnetic and plasmonic portions significantly prevents the decline in relaxivity of the Fe3O4 core caused by the Au layer. Moreover, in addition to conferring high near‐infrared absorption to plasmonic component, the hollow cavity and the pores in the outer shell can also provide a large storage space and release channels for anticancer drugs. Furthermore, the multicomponent nanoparticles (NPs) still have a compact size of less than 100 nm to ensure efficient tumor accumulation. Taken together, the yolk–shell Fe3O4@Au NPs can be regarded as an ideal magnetic–plasmonic theranostic platform for magnetic resonance/photoacoustic/positron emission tomography multimodal imaging and light‐activated chemothermal synergistic therapy.  相似文献   

10.
2D mesoporous materials fabricated via the assembly of nanoparticles (NPs) not only possess the unique properties of nanoscale building blocks but also manifest additional collective properties due to the interactions between NPs. In this work, reported is a facile and designable way to prepare free‐standing 2D mesoporous gold (Au) superstructures with a honeycomb‐like configuration. During the fabrication process, Au NPs with an average diameter of 5.0 nm are assembled into a superlattice film on a diethylene glycol substrate. Then, a subsequent thermal treatment at 180 °C induces NP attachment, forming the honeycomb‐like ordered mesoporous Au superstructures. Each individual NP connects with three neighboring NPs in the adjacent layer to form a tetrahedron‐based framework. Mesopores confined in the superstructure have a uniform size of 3.5 nm and are arranged in an ordered hexagonal array. The metallic bonding between Au NPs increases the structural stability of architected superstructures, allowing them to be easily transferred to various substrates. In addition, electron energy‐loss spectroscopy experiments and 3D finite‐difference time‐domain simulations reveal that electric field enhancement occurs at the confined mesopores when the superstructures are excited by light, showing their potential in nano‐plasmonic applications.  相似文献   

11.
Great opportunities emerge not only in the generation of anisotropic plasmonic nanostructures but also in controlling their orientation relative to incident light. Herein, a stepwise seeded growth method is reported for the synthesis of rod‐shaped plasmon nanostructures which are vertically self‐aligned with respect to the surface of colloidal substrates. Anisotropic growth of metal nanostructure is achieved by depositing metal seeds onto the surface of colloidal substrates and then selectively passivating the seed surface to induce symmetry breaking in the subsequent seed‐mediated growth process. The versatility of this method is demonstrated by producing nanoparticle dimers and linear trimers of Au, Au–Ag, Au–Pd, and Au–Cu2O. Further, this unique method enables the automatic vertical alignment of the resulting plasmonic nanostructures to the surface of the colloidal substrate, thereby making it possible to design magnetic/plasmonic nanocomposites that allow the dynamic tuning of the plasmon excitation by controlling their orientation using an external magnetic field. The controlled anisotropic growth of colloidal plasmonic nanostructures and their dynamic modulation of plasmon excitation further allow them to be conveniently fixed in a thin polymer film with a well‐controlled orientation to display polarization‐dependent patterns that may find important applications in information encryption.  相似文献   

12.
Significant advances have been made in photonic integrated circuit technology, similar to the development of electronic integrated circuits. However, the miniaturization of cavity resonators, which are the essential components of photonic circuits, still requires considerable improvement. Over the past decades, various optical cavities have been utilized to implement next-generation light sources in photonic circuits with low energy, high data traffic, and integrable physical sizes. Nevertheless, it has been difficult to reduce the size of most commercialized cavities beyond the diffraction limit while maintaining high performance. Herein, recent advancements in subwavelength metallic cavities that can improve performance, even with the use of lossy plasmonic modes, are reviewed. The discussion is divided in three parts according to light engineering methods: subwavelength metal-clad cavities engineered using intermediate dielectric cladding; implementation of plasmonic cavities and waveguides using plasmonic crystals; and development of deep-subwavelength plasmonic waveguides and cavities using geometric engineering. A direction for further developments in photonic integrated circuit technology is also discussed, along with its practical application.  相似文献   

13.
Backward waves with wave‐front propagation opposite in direction to that of energy flow have attracted considerable interest in the context of photonic metamaterials. However, switching between forward and backward waves in the same frequency range has remained a challenge. Here, on a platform of coupled designer surface plasmon resonators in the microwave regime, multiband forward/backward switching of plasmonic wave propagation is demonstrated. This approach makes use of sign‐reversal coupling that occurs when switching the coupling configuration between tightly confined photonic modes. Direct experimental measurements of plasmon dispersion curves confirm the forward/backward propagation of plasmonic waves in the same frequency range. This study provides a solution to forward/backward switching of subwavelength plasmonic wave propagation, and may find potential applications in photonic integrated systems.  相似文献   

14.
Magnetic‐plasmonic nanoparticles have received considerable attention for widespread applications. These nanoparticles (NPs) exhibiting surface‐enhanced Raman scattering (SERS) activities are developed due to their potential in bio‐sensing applicable in non‐destructive and sensitive analysis with target‐specific separation. However, it is challenging to synthesize these NPs that simultaneously exhibit low remanence, maximized magnetic content, plasmonic coverage with abundant hotspots, and structural uniformity. Here, a method that involves the conjugation of a magnetic template with gold seeds via chemical binding and seed‐mediated growth is proposed, with the objective of obtaining plasmonic nanostructures with abundant hotspots on a magnetic template. To obtain a clean surface for directly functionalizing ligands and enhancing the Raman intensity, an additional growth step of gold (Au) and/or silver (Ag) atoms is proposed after modifying the Raman molecules on the as‐prepared magnetic‐plasmonic nanoparticles. Importantly, one‐sided silver growth occurred in an environment where gold facets are blocked by Raman molecules; otherwise, the gold growth is layer‐by‐layer. Moreover, simultaneous reduction by gold and silver ions allowed for the formation of a uniform bimetallic layer. The enhancement factor of the nanoparticles with a bimetallic layer is approximately 107. The SERS probes functionalized cyclic peptides are employed for targeted cancer‐cell imaging and separation.  相似文献   

15.
Plasmon‐mediated photocatalytic systems generally suffer from poor efficiency due to weak absorption overlap and thus limited energy transfer between the plasmonic metal and the semiconductor. Herein, a near‐ideal plasmon‐mediated photocatalyst system is developed. Au/CdSe nanocrystal clusters (NCs) are successfully fabricated through a facile emulsion‐based self‐assembly approach, containing Au nanoparticles (NPs) of size 2.8, 4.6, 7.2, or 9.0 nm and CdSe quantum dots (QDs) of size ≈3.3 nm. Under visible‐light irradiation, the Au/CdSe NCs with 7.2 nm Au NPs afford very stable operation and a remarkable H2‐evolution rate of (10× higher than bare CdSe NCs). Plasmon resonance energy transfer from the Au NPs to the CdSe QDs, which enhances charge‐carrier generation in the semiconductor and suppresses bulk recombination, is responsible for the outstanding photocatalytic performance. The approach used here to fabricate the Au/CdSe NCs is suitable for the construction of other plasmon‐mediated photocatalysts.  相似文献   

16.
Photoelectrochemical (PEC) water splitting is a promising approach for producing hydrogen without greenhouse gas emissions. Despite decades of unceasing efforts, the efficiency of PEC devices based on earth‐abundant semiconductors is still limited by their low light absorption, low charge mobility, high charge‐carrier recombination, and reduced diffusion length. Plasmonics has recently emerged as an effective approach for overcoming these limitations, although a full understanding of the involved physical mechanisms remains elusive. Here, the reported plasmonic effects are outlined, such as resonant energy transfer, scattering, hot electron injection, guided modes, and photonic effects, as well as the less investigated catalytic and thermal effects used in PEC water splitting. In each section, the fundamentals are reviewed and the most representative examples are discussed, illustrating possible future developments for achieving improved efficiency of plasmonic photoelectrodes.  相似文献   

17.
Colloidal metal nanocrystals with strong, stable, and tunable localized surface plasmon resonances (SPRs) can be useful in a corrosive environment for many applications including field‐enhanced spectroscopies, plasmon‐mediated catalysis, etc. Here, a new synthetic strategy is reported that enables the epitaxial growth of a homogeneously alloyed AuAg shell on Au nanorod seeds, circumventing the phase segregation of Au and Ag encountered in conventional synthesis. The resulting core–shell structured bimetallic nanorods (AuNR@AuAg) have well‐mixed Au and Ag atoms in their shell without discernible domains. This degree of mixing allows AuNR@AuAg to combine the high stability of Au with the superior plasmonic activity of Ag, thus outperforming seemingly similar nanostructures with monometallic shells (e.g., Ag‐coated Au NRs (AuNR@Ag) and Au‐coated Au NRs (AuNR@Au)). AuNR@AuAg is comparable to AuNR@Ag in plasmonic activity, but that it is markedly more stable toward oxidative treatment. Specifically, AuNR@AuAg and AuNR@Ag exhibit similarly strong signals in surface‐enhanced Raman spectroscopy that are some 30‐fold higher than that of AuNR@Au. When incubated with a H2O2 solution (0.5 m ), the plasmonic activity of AuNR@Ag immediately and severely decayed, whereas AuNR@AuAg retained its activity intact. Moreover, the longitudinal SPR frequency of AuNR@AuAg can be tuned throughout the red wavelengths (≈620–690 nm) by controlling the thickness of the AuAg alloy shell. The synthetic strategy is versatile to fabricate AuAg alloyed shells on different shaped Au, with prospects for new possibilities in the synthesis and application of plasmonic nanocrystals.  相似文献   

18.
Photo‐electrochemical water splitting is a very promising and environmentally friendly route for the conversion of solar energy into hydrogen. However, the solar‐to‐H2 conversion efficiency is still very low due to rapid bulk recombination of charge carriers. Here, a photonic nano‐architecture is developed to improve charge carrier generation and separation by manipulating and confining light absorption in a visible‐light‐active photoanode constructed from BiVO4 photonic crystal and plasmonic nanostructures. Synergistic effects of photonic crystal stop bands and plasmonic absorption are observed to operate in this photonic nanostructure. Within the scaffold of an inverse opal photonic crystal, the surface plasmon resonance is significantly enhanced by the photonic Bragg resonance. Nanophotonic photoanodes show AM 1.5 photocurrent densities of 3.1 ± 0.1 mA cm?2 at 1.23 V versus RHE, which is among the highest for oxide‐based photoanodes and over 4 times higher than the unstructured planar photoanode.  相似文献   

19.
Recently, polymer‐coated magnetite (Fe3O4) nanoparticles (NPs) are extensively studied for applications in therapeutics or diagnostics using photothermal effect. Therefore, it is essential to understand the interactions between Fe3O4 NPs and polymers when optical stimuli are applied. Herein, the photonic reactions of Fe3O4 NPs and polymer composites upon application of a 780 nm multiphoton laser are analyzed. The photonic reactions produce unique results including fluorescence from conformationally changed polymer and low‐temperature phase transformation of Fe3O4 NPs. Typically, π‐conjugated chains are formed, inducing fluorescence through a series of main and side‐chain cleavage reactions of polymers with the aliphatic chain. In addition, fluorescence is detected in the cellular system by photonic reactions between Fe3O4 NPs and biomolecules. After multiphoton laser irradiation, light emission is detected near the intracellular Fe3O4 NPs, and a stronger intensity is observed in large‐sized NPs.  相似文献   

20.
Microcapsules consisting of hydrogel shells cross‐linked by glucosamine–boronate ester complexes and duplex nucleic acids, loaded with dyes or drugs and functionalized with Au nanoparticles (Au NPs) or Au nanorods (Au NRs), are developed. Irradiation of Au NPs or Au NRs results in the thermoplasmonic heating of the microcapsules, and the dissociation of the nucleic acid cross‐linkers. The separation of duplex nucleic acid cross‐linkers leads to low‐stiffness hydrogel shells, allowing the release of loads. Switching off the light‐induced plasmonic heating results in the regeneration of stiff hydrogel shells protecting the microcapsules, leading to the blockage of release processes. The thermoplasmonic release of tetramethylrhodamine‐dextran, Texas Red‐dextran, doxorubicin‐dextran (DOX‐D), or camptothecin‐carboxymethylcellulose (CPT‐CMC) from the microcapsules is introduced. By loading the microcapsules with two different drugs (DOX‐D and CPT‐CMC), the light‐controlled dose release is demonstrated. Cellular experiments show efficient permeation of Au NPs/DOX‐D or Au NRs/DOX‐D microcapsules into MDA‐MB‐231 cancer cells and inefficient uptake by MCF‐10A epithelial breast cells. Cytotoxicity experiments reveal selective thermoplasmon‐induced cytotoxicity of the microcapsules toward MDA‐MB‐231 cancer cells as compared to MCF‐10A cells. Also, selective cytotoxicity towards MDA‐MB‐231 cancer cells upon irradiation of the Au NPs‐ and Au NRs‐functionalized microcapsules at λ = 532 or 910 nm is demonstrated.  相似文献   

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