Shell-isolated nanoparticleenhanced Raman spectroscopy: Insight from COMSOL simulations
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1 Shell-isolated nanoparticleenhanced Raman spectroscopy: Insight from COMSOL simulations Song-Yuan Ding, Jun Yi, En-Ming You, and Zhong-Qun Tian , Shanghai Excerpt from the Proceedings of the 2016 COMSOL Conference in Shanghai
2 Outline Principle of surface-enhanced Raman spectroscopy for surface analysis of materials Features of hybrid structure with gold nanoparticle aggregates electromagnetically coupled with a flat metal surface Some tricks for the COMSOL simulation of nanooptics.
3 Everything is surface and interface Adhesion Wear and wetting Friction Catalysis Corrosion electrochemistry Handbook of surfaces and interfaces of materials; J. Surf. Interf. Mater. 1, 1-3 (2013). 3
4 The enhanced local field and induced dipole at ω 0 due to NPs First step (G 1 ) Second step (G 2 ) If there were no mutual excitation from m-nps system at ω R, no enhanced apparent Raman polarizability exist G 1~ E loc ω 0 /E 0 ω 0 2 G 2~ E loc ω R /E 0 ω R 2 Incident light at ω 0 Normal Raman SERS I SERS /I Raman = G 1 G 2 ~ E loc ω 0 /E 0 ω 0 4
5 a b Methods Nanostructures Discovery of SERS , , c d e f Applied Materials Papers SERS-Active materials Overcoating materials Unperturbed materials High-active: Ag, Au, Cu, Z Li, Na, K, In, Al Ni, Co, Fe, Pt, Pd, Rh, Polymers GaAs, Si Weak-active: Pt, Fe, Co, Ni, Ru, Rh Pd Liquid crystals, carbon nanotube, geological materials, pigments and pottery SiO 2, Al 2 O 3, MnO 2, TiO 2 Graphene Graphene, Si, h-bn, etc. CdS, Ge, Si nanowire, BaTiO 3 nanorod bio-membrane, etc. ~ 500 ~ 1,600 ~ 5,300 ~ 25,000
6 1 st and 2 nd generation hotspots Materials are hard to be squeezed into hotspot in nanogap! Any new concept of hotspot for surface analysis of materials?
7 The 3 rd generation hotspots generated by hybrid structures with nanostructures and probe materials No. <G sub > G max,sub G max,np a-i *10 3 a-ii 1.3* *10 4 b-i 1.5* *10 7 b-ii 7.3* *10 6 c-i 1.0* * *10 7 c-ii 1.0* * *10 7 d-i 1.7* * *10 6 d-ii 2.1* * *10 7 a(np) = 60 nm, t(sio 2 ) = 2 nm g(np-np) = 2 nm, g(np-sub) = 1 nm Ding, Yi, Li, et al, Nat. Rev. Mater. 2016, 1,
8 Fano-resonance Plasmon-enhanced Raman Scattering of nanospheres-flat Surface Systems? Norm E Surface Charge density at 650 nm Fano Resonance: Coupled dipole of Nanoparticles induce the imaginary dipole on the metal or dielectric surfaces, to form a magnetic-dipole-like mode. It is the plasmonic dark mode with less irradiative efficiency, but with strong near field.
9 SHINERS works on single crystal surfaces of different materials beyond Au, Ag, Cu metals Au Cu Ni Ag Norm E Extinction(a.u.) Point A, norme Wavelength (nm) Au Cu Ni Ag 150 Point B, norme Au Cu Ni Ag norme (V/m) norme (V/m) Wavelength (nm) Ding, Yi and Tian, Surf. Sci., 631 (2015) Wavelength (nm)
10 SHINERS of Si-H 260nm 360nm 440nm 560nm 600nm 700nm (a) Si(111) treated with 98% H 2 SO 4 (b) treated with 30% HF solution, (c) treated with O 2 plasma Li et al, Nature 464, (2010); Ding, Yi and Tian, Surf. Sci., 631 (2015)
11 There is always a node line underneath a single particle on a flat metal surface 0 degree 11
12 75 degree, 12
13 PERS hot domain? Extinction Average Enhancement 800 Extinction Average Enhancement Wavelength (nm) 55nm AuNP, d(np-np) = 4 nm, d(np-ausurf)= 2 nm
14 PERS hot domain? Extinction Average Enhancement 4000 Extinction Average Enhancement Wavelength (nm)
15 Hot domains created by AuNS 7 on a flat Au surface Extinction Average Enhancement Extinction Average Enhancement Wavelength (nm)
16 16
17 Good directional receiving and emission of AuNPs-Au surfaces nm 8nm 12nm 16nm 20nm 24nm nm 8nm 12nm 16nm 20nm 24nm ZX plane ZY plane 0 Extinction (a.u.) Extinction Average Intensity Average Intensity (V/m)^ Wavelength(nm) 17
18 Conclusion COMSOL is very useful for the design of novel nanostructures for surface-enhanced Raman spectroscopies Care should be taken for evaluation of near-field on the surface of nanostructures Tricks on the simulation of a point dipolar source. 19
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