Supplementary Figure S1 Anticrossing and mode exchange between D1 (Wood's anomaly)

Transcription

1 Supplementary Figure S1 Anticrossing and mode exchange between D1 (Wood's anomaly) and D3 (Fabry Pérot cavity mode). (a) Schematic (top) showing the reflectance measurement geometry and simulated angle-resolved reflectance spectra (bottom) of the GMRA (a = 610 nm, h = 510 nm, l = 285 nm, t = 110 nm) with the incidence angle varying from 8 to 36 at a step of 1. The red dashed line denotes (1, 0) Wood's anomaly in air. As the incidence angle is increased, D3, which results from the Fabry Pérot-type cavity formed between the upper gold cap layer and lower perforated gold film layer, is split by Wood's anomaly in the spectral range of 700 to 900 nm. (b) Electric field distribution of E y at the incidence angle of 31 (after the anticrossing) and 25 (before the anticrossing) for the points A, B, C and D, as marked in a, respectively. The scale bar for the electric field distribution is at the linear scale. Clearly, at θ = 31, the E y distribution of the lower-energy mode (B, λ = 941 nm) is similar to that of the higherenergy mode (C, λ = 842 nm) at θ = 25. Both are featured with a lateral dipolar pattern on the gold cap. Similarly, at θ = 31, the E y distribution of the higher-energy mode (A, λ = 875 nm) is nearly the same as that of the lower-energy mode (D, λ = 935 nm) at θ = 25. Both are featured with the vertical coupling between the upper gold cap layer and the lower perforated gold film layer, which is characteristic of the Fabry Pérot cavity mode. 1

2 Supplementary Figure S2 Angle-resolved reflectance spectra measured in air. The incidence angle was varied from 36 to 68. The sizes of the GMRA are a = 610 nm, h = 510 nm, l = 285 nm, t = 110 nm. Supplementary Figure S3 Angle-resolved reflectance spectra measured in air under p- polarized incident light. The incidence angle was varied from 8 to 36 at a step of 1. The sizes of the GMRA are a = 610 nm, h = 510 nm, l = 285 nm, t = 110 nm. 2

3 Supplementary Figure S4 Determination of the FWHM value of the dip. The reflectance value at the dip is denoted with R 2, and that at the left shoulder is denoted with R 1. The FWHM value is then taken at the reflectance value of (R 1 + R 2 )/2, as indicated with the doubly arrowed line. 3

4 Supplementary Figure S5 Reflectance spectra of the GMRA and the shifts of D1. (a) Reflectance spectra recorded in air (black, the incidence angle = 33.5 ) and water (red, the incidence angle = 33.3 ). (b) Variation of the spectral position of D1 with the refractive index. The sizes of the GMRA are a = 610 nm, h = 510 nm, l = 285 nm, t = 110 nm. The wavelength of D1 in air at an incidence angle of 33.3 was obtained from a pre-measured linear calibration curve between the spectral position of D1 and the incidence angle. Linear fitting of the data points in the refractive index range of to (blue line) gives rise to an index sensitivity of 1015 nm RIU 1. The FOM value is therefore The refractive index sensitivity obtained from linear fitting in the index range of 1 to (red line) is 893 nm RIU 1, which results in a FOM value of The slight reductions in the index sensitivity and FOM value might be due to that the dip arises from the coupling between Wood's anomaly and D3 in air and the coupling between Wood's anomaly and D4 in the liquids. The interaction of a plasmon mode with the surrounding dielectric medium is affected by its spatial electric field distribution. The field distributions for D3 and D4 are different even though both of them result from the interaction between the LSPRs of the gold cap array and perforated gold film. 4

5 Supplementary Figure S6 Surface regeneration of the GMRA during Cyt c detection. (a) Reflectance spectra recorded upon Cyt c adsorption at 1.75 M and after regeneration for three cycles. (b) Variation of the Dip position during the three cycles of Cyt c adsorption and subsequent regeneration. The sizes of the GMRA are a = 610 nm, h = 480 nm, l = 265 nm, t = 110 nm. Supplementary Figure S7 Spectral positions of the dip extracted from the reflectance spectra shown in Fig. 5c. 5

6 Supplementary Figure S8 Spectral shifts of D1 measured when the change in the weight percentage of glycerol and thus the refractive index of the solution is very small. (a) Spectral shift (blue squares) of D1 as a function of the solution index. The incidence angle from air to the solution is kept unchanged. The red line is the linear fitting of the data measured when the solution index change is large and the incidence angle from air to the solution is adjusted. The corresponding weight percentage of glycerol for the four data points are 0%, %, %, and %, respectively. (b) Spectral shift (black squares) of D1 measured in water as the incidence angle from the solution to the GMRA is varied. The reference point for the spectral shifts is that at The red line is linear fitting. (c) Corrected spectral shift (blue squares) of D1 as a function of the solution index. The correction is based on the line in b. The sizes of the GMRA are a = 610 nm, h = 510 nm, l = 285 nm, t = 110 nm. The error bars in a represent standard deviations calculated from three data points measured at each weight percentage of glycerol as mentioned in the Methods section. Each error bar in c is equal to the corresponding one in a, since the data points are only shifted vertically. 6

7 Supplementary Figure S9 Schematic showing the geometry for measuring the reflectance spectrum of the GMRAs at normal incidence. The final reflectance spectra of the GMRA were corrected by dividing them with the spectrum measured on a silver mirror. Supplementary Figure S10 Representative reflectance spectra of the GMRA measured in water after the rinsing process during the refractive index sensitivity measurement. The sizes of the GMRA are a = 610 nm, h = 510 nm, l = 285 nm, t = 110 nm. 7

8 Supplementary Figure S11 Simulated reflectance spectra of the GMRAs with different rounding degrees for the gold caps, pillars, and gold holes under normal incidence in air. (a) Simulated (solid lines) and measured (dashed line) reflectance spectra. (b) Schematics of the structures used in the FDTD simulations. The top, middle, and bottom represent the GMRAs with rounded square, circular, and unrounded square gold caps, respectively. The sizes of the GMRAs are all a = 610 nm, h = 510 nm, l = 285 nm, t = 110 nm. For the circular one, l refers to the diameter. Supplementary Figure S12 Experimental and simulated reflectance spectra of the GMRA under normal incidence in air. The dielectric functions of gold obtained from Drude model and from the data by Johnson and Christy were utilized in the FDTD simulations. The sizes of the GMRA are a = 610 nm, h = 510 nm, l = 285 nm, and t = 110 nm. 8

9 Supplementary Table S1 Summary of the refractive index sensitivities and FOM values of plasmonic metal nanostructures for LSPR sensors without the occurrence of Fano resonance. Reference a Nanostructures Single or ensemble Resonance wavelength (nm/ev) b FWHM (nm/ev) b Sensitivity (nm/ev per RIU) b Wang, Langmuir 2008, Au nanospheres Ensemble 527/ / / Wang, Langmuir 2008, Au nanostars Ensemble 1141/ / / Halas, J. Phys. Chem. (Au core)/(sio 2 shell) Ensemble 770/ / / B 2004, 108, Xia, Anal. Chem. (Au core)/(aus shell) Ensemble 700/ / / , 74, 5297 Halas, Nano Lett. Au nanowires Ensemble 1600/ / / , 6, 827 Mulvaney, Langmuir Au nanospheres Ensemble 530/ / / , 10, 3427 Raschke, Nano Lett. (Au core)/(aus shell) Single 660/ / / , 4, 1853 Wang, Langmuir 2008, Au nanocubes Ensemble 538/ / / Van Duyne, Nano Lett. Ag nanocubes Single 510/ / / , 5, 2034 Wang, Langmuir 2008, Au nanorods Ensemble 846/ / / Wang, Langmuir 2008, Au nanobipyramids Ensemble 645/ / / Van Duyne, J. Am. Ag nanoprisms Ensemble 564/ / / Chem. Soc. 2001, 123, 1471 Hafner, Nano Lett. Au nanostars Single 675/ / / , 6, 683 Wang, Langmuir 2008, Au nanorods Ensemble 728/ / / Mock, Nano Lett. Ag nanospheres Single 520/ / / , 3, 485 Wang, Langmuir 2008, Au nanorods Ensemble 653/ / / Wang, Langmuir 2008, Au nanobipyramids Ensemble 735/ / / Van Duyne, Nano Lett. Ag nanoparticles Single 585/ / / , 3, 1057 Wang, Langmuir 2008, Au nanobipyramids Ensemble 886/1.4 93/ / Mock, Nano Lett. Ag nanoprisms Single 760/ / / , 3, 485 Wang, Langmuir 2008, Au nanobipyramids Ensemble 1096/ / / Hafner, Nano Lett. Au nanostars Single 770/ / / , 6, 683 Van Duyne, Nano Lett. Ag nanocubes on Single 430/ / / FOM 9

10 2005, 5, 2034 substrates a Only the last name of the corresponding author or a representative corresponding author is given. b The number before the slash refers to wavelength in nm, and that after the slash refers to energy in ev. Supplementary Table S2 Summary of the refractive index sensitivities and FOM values of plasmonic metal nanostructures for LSPR sensors with Fano resonance. Reference a Nanostructures Single or ensemble Huang, Appl. Phys. Lett. 2012, 100, Verellen, Nano Lett. 2011, 11, 391 Nordlander, Nano Lett. 2010, 10, 3184 Lodewijks, Nano Lett. 2012, 12, 1655 Atwater, ACS Nano 2011, 5, 8167 Atwater, ACS Nano 2011, 5, 8167 Jin, Plasmonics 2013, 8, 885 Lodewijks, Nano Lett. 2012, 12, 1655 Nordlander, Nano Lett. 2011, 11, 1657 Cattoni, Nano Lett. 2011, 11, 3557 Resonance wavelength FWHM Sensitivity FOM nm ev nm ev nm per RIU ev per RIU Au nanorings Array "XI" nanostructures Single Au nanodisks Cluster Au nanodisks Array Split-ring resonators Array Split-ring resonators with bars Single Au nanoprisms Prism dimer Au nanorings Array Ag nanocubes Single Microcavities Array a Only the last name of the corresponding author or a representative corresponding author is given. 10