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.

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.