High Raman peak intensities have been observed in small periodicities as illustrated in Figure5.9 and Figure5.6 in the essence that the x period 500 nm is well coupled
in an efficient way with the Raman excitation laser. Although there is the red shift of surface lattice resonances as shown in Figure 5.6, array 500x580 has small shift of SLR from the diffractive order (crosscut). Figure5.7 shows that 600 nm y period is coupled well to the Raman shift of the molecules (Rhodamine 6G) at 875 nm.
Chapter VI
Conclusions
In this work, we studied surface enhanced Raman scattering in plasmonic nanopar-ticle lattices. We have shown that, radiative coupling can be used to engineer and enhance plasmonic effects. Tunability of the resonance wavelength via periodicity was demonstrated for both gold and silver nanoparticle arrays. We have also re-ported two dimensional tunability via px and py periodicity, providing a universal method for creating and utilizing double resonances. We observed additional res-onance wavelength from the transmission plots of gold sample which is associated with the diagonal periodicity. Unfortunately, silver sample had poor resolution in the transmission plot we could not observe the second resonance, however, with good sample fabrication in the future we will be able to see it.
The radiative coupling was studied and verified via angle and wavelength resolved transmission measurements, where the periodicity dependent effects were clearly ob-served, following the expected dependency on thepx andpy. This was accomplished for both gold and silver samples.
This work has shown significant merit specifically in Raman spectroscopy. We were able to match periodicitypxto Raman excitation wavelength and periodicitypy
to the Raman shift of the analyte, namely R6G molecules. This was experimentally demonstrated such that x period of 500 nm is coupled in an efficient way with the Raman excitation laser, while 600 nm y period is coupled well to the Raman shift of Rhodamine 6G at 890 nm (1510 cm−1). Generally, Raman peaks were observed at 1310 cm−1, 1365 cm−1 and 1510 cm−1 where the Raman excitation wavelength used was 785 nm.
Further, we were able to show the periodicity (px and py) related effects
signif-icantly improved SERS effect. This was proved from comparing the SERS from an ordered array against the random samples. That being said, we have random sam-ples, “Random-1” and “Random-2”, despite of having equal particle density, their inter-spacing distance between particles were different. Higher enhancements was achieved from “Random-1” where the particle positions were entirely random such that arbitrarily small gaps between particles was inevitable, hence inducing plas-monic hotspots. On the other hand, “Random-2” in which the inter-particle distance was kept above 50 nm to exclude plasmonic hotspots, there was less enhancement compared to both an ordered array and “Random-1”. On top of that, we have shown that the R6G film only did not show any observable Raman signal, confirming earlier findings of plasmonic enhancement of SERS.
Due to the time constraints, we have not been able to accomplish all objectives of the work. However, the future prospects of the work will prioritize on determining the Q-factor from the linewidth of the transmision plots. Further optimization of thepx,py (and possible the diagonal periodicity) will be made for obtaining a better match between the excitation laser as well as Raman fingerprint region of variety of analytes. We also aim to reduce the angular range of excitation laser to more selectively excite the SLR resonance. Further, we proceed to test the samples with perpendicular polarizations between the excitation and detection, as the radiative coupling between x and y directions are expected to have opposite polarizations. We have demonstrated a universal method to engineer and utilize double resonances in 2 dimensional broken symmetry plasmonic in lattices, that can be utilized not only in Raman, but in any other nano-optical platform, for instance fluorescence enhance-ment, second harmonic generation and establishing multimode lasing in plasmonic nanoparticle arrays, to name a few.
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Appendix A
Radiation effect in x periodicity - silver sample
(a) (b)
500x580
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
Figure A.1: Transmission plots
(e) (f)
500x596
600 700 800 900
[nm]
50 100 150 200
Intensity [a.u.]
20 40 60 80
100 500x600
600 700 800 900
[nm]
50 100 150 200
Intensity [a.u.]
20 40 60 80 100
Figure A.2: Transmission plots
(g) (h)
510x580
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
Figure A.3: Transmission plots
(m) (n)
520x580
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
Figure A.4: Transmission plots
(s) (t)
530x580
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
Figure A.5: Transmission plots
(y) (z)
540x580
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
Figure A.6: Transmission plots
(e) (f)
500x580Random-1
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
Figure A.7: Random arrays
Appendix B
Radiation effect in y periodicity - silver sample
(a) (b)
500x580
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
Figure B.1: Transmission plots
(e) (f)
500x596
600 700 800 900
[nm]
50 100 150 200
Intensity [a.u.]
20 40 60 80
100 500x600
600 700 800 900
[nm]
50 100 150 200
Intensity [a.u.]
20 40 60 80 100
Figure B.2: Transmission plots
(m) (n)
510x580
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
Figure B.3: Transmission plots
(s) (t)
520x580
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
Figure B.4: Transmission plots
(y) (z)
530x580
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
Figure B.5: Transmission plots
(d) (e)
540x580
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
Figure B.6: Transmission plots
(j) (k)
500x580Random-1
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
600 700 800 900
[nm]
Figure B.7: Random arrays
Appendix C
Raman spectra - y polarized laser light
(a) (b)
1200 1400 1600 1800
Raman shift (1/cm)
1200 1400 1600 1800
Raman shift (1/cm)
1200 1400 1600 1800
Raman shift (1/cm)
1200 1400 1600 1800
Raman shift (1/cm)
Figure C.1: Raman spectra for periodic arrays
(e) (f)
1200 1400 1600 1800
Raman shift (1/cm)
1200 1400 1600 1800
Raman shift (1/cm)
1200 1400 1600 1800
Raman shift (1/cm)
1200 1400 1600 1800
Raman shift (1/cm)
Figure C.2: Raman spectra for periodic arrays
(i) (j)
1200 1400 1600 1800
Raman shift (1/cm)
1200 1400 1600 1800
Raman shift (1/cm)
1200 1400 1600 1800
Raman shift (1/cm)
1200 1400 1600 1800
Raman shift (1/cm)
Figure C.3: Raman spectra for periodic arrays
(m) (n)
1200 1400 1600 1800
Raman shift (1/cm)
1200 1400 1600 1800
Raman shift (1/cm)
1200 1400 1600 1800
Raman shift (1/cm)
1200 1400 1600 1800
Raman shift (1/cm)
Figure C.4: Raman spectra for periodic arrays
(q) (r)
1200 1400 1600 1800
Raman shift (1/cm)
1200 1400 1600 1800
Raman shift (1/cm)
1200 1400 1600 1800
Raman shift (1/cm)
1200 1400 1600 1800
Raman shift (1/cm)
Figure C.5: Raman spectra for periodic arrays
(a) (b)
1200 1400 1600 1800
Raman shift (1/cm)
1200 1400 1600 1800
Raman shift (1/cm)
1200 1400 1600 1800
Raman shift (1/cm)
1200 1400 1600 1800
Raman shift (1/cm)
Raman shift (1/cm)