Efficient photoinduced charge transfer (PICT) resonance is crucial to the surface-enhanced Raman scattering (SERS) performance of metal oxide substrates. Herein, we venture into the hot-electron injection strategy to achieve unprecedented enhanced PICT efficiency between substrates and molecules. A heterojunction array composed of plasmonic MoO 2 and semiconducting WO 3−x is designed to prove the concept. The plasmonic MoO 2 generates intense localized surface plasmon resonance under illumination, which can generate near-field Raman enhancement as well as accompanied plasmon-induced hot-electrons. The hot-electron injection in direct interfacial charge transfer and plasmon-induced charge transfer process can effectively promote the PICT efficiency between substrates and molecules, achieving a record Raman enhancement factor among metal oxide substrates (2.12 × 10 8 ) and the ultrasensitive detection of target molecule down to 10 −11 M. This work demonstrates the possibility of hot-electron manipulation to realize unprecedented Raman enhancement in metal oxides, offering a cutting-edge strategy to design high-performance SERS substrates.
For the semicircular plasmonic lens, the spiral phase is the origin of the spin-dependent surface plasmon polariton (SPP) focusing. By counterbalancing the spin-dependent spiral phase with another spiral phase or Pancharatnam-Berry phase, we realized the SPP focusing independent from the spin states of the excitation light. Analyses based on both Huygens-Fresnel principle for SPPs and numerical simulations prove that the position, intensity, and profile of the SPP focuses are exactly the same for different spin states. Moreover, the spin-independent SPP focusing is immune from the change of the radius, the central angle, and the shape of the semicircular slit. This study not only further reveals the mechanism of spin-dependent SPP devices but also provides effective approaches to overcome the influence of spin states on the SPPs field.
Noble-metal-free surface-enhanced Raman scattering (SERS) substrates have attracted great attention for their abundant sources, good signal uniformity, superior biocompatibility, and high chemical stability. However, the lack of controllable synthesis and fabrication of noble-metal-free substrates with high SERS activity impedes their practical applications. Herein, we propose a general strategy to fabricate a series of planar transition-metal nitride (TMN) SERS chips via an ambient temperature sputtering deposition route. These planar TMN (tungsten nitride, tantalum nitride, and molybdenum nitride) chips show remarkable Raman enhancement factors (EFs) with ~10 5 owing to efficient photoinduced charge transfer process between TMN chips and probe molecules. Further, structural engineering of 2 these TMN chips is used to improve their SERS activity. Benefiting from the synergistic effect of charge transfer process and electric field enhancement by constructing nanocavity structure, the Raman EF of WN nanocavity chips could be greatly improved to ∼1.29 × 10 7 , which is an order of magnitude higher than that of planar chips. Moreover, we also design the WN/monolayer MoS2 heterostructure chips. With the increase of surface electron density on the upper WN and more exciton resonance transitions in the heterostructure, a ∼1.94 × 10 7 level EF and a 5 × 10 -10 M level detention limit could be achieved. Our results provide important guidance for the structural design of ultrasensitive noble-metal-free SERS chips.
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