Low absorption losses of strongly coupled surface plasmons in nanoparticle assemblies

Wei-Shun Changa, Britain A. Willinghama, Liane S. Slaughtera, Bishnu P. Khanala, Leonid Vigdermana, Eugene R. Zubareva, and Stephan Linka,b,1
a

Department of Chemistry, and bDepartment of Electrical and Computer Engineering, Laboratory for Nanophotonics, Rice University, Houston, TX 77005

Edited by Federico Capasso, Harvard University, Cambridge, MA, and approved September 26, 2011 (received for review August 20, 2011)

nanoparticle self-assembly photothermal heterodyne imaging surface plasmon resonance single particle spectroscopy dark-field imaging

lasmonic antennas can convert optical radiation into intense local field distributions or enable coupling to guided modes that are confined to subwavelength dimensions (14). Strong surface plasmon (SP) coupling between neighboring nanoparticles (NPs) also leads to large enhancements of electromagnetic fields, which benefit various applications such as waveguides (5, 6), nano-antennas (79), field enhanced spectroscopies (1012), and biological sensors (4, 13, 14). The interparticle coupling resulting from near-field interactions between closely spaced NPs is inversely proportional to d3 where d is the distance between the NPs (6). The largest local field enhancements are indeed found for the smallest interparticle distances (11, 15). Extremely small interparticle gaps of a few nanometers can be achieved in selfassembled nanostructures (1619), opening up new paths for the design of plasmonic devices. With bottom-up assembly, precise periodic positioning of the NPs is more difficult and hence structures with a distribution of NP gaps are created. However, high throughput patterning for large area fabrication at reduced costs make NP assemblies attractive alternatives to structures made by conventional top-down approaches (20). For the system studied here, SI Appendix, Fig. S1 shows an example of a periodic array of rings assembled from a chloroform solution of 40 nm gold NPs. In addition, the recent use of correlated electron and optical microscopy on individual NP assemblies is making it possible to decipher the effects of local NP ordering and symmetry breaking on the collective optical response (21). Independent of the plasmonic nanostructure, absorption by the metal is thought to be the main mechanism for plasmon energy dissipation due to nonradiative relaxation processes (3, 2224). Substantial attenuation of electromagnetic waves due to ohmic loss is therefore the major issue for applications such as
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Results and Discussion Rings of polystyrene-coated 40-nm gold NPs were fabricated on glass slides as described previously (31). Polyvinyl alcohol films with a refractive index of 1.5 were spin-cast on top of the rings to provide a homogenous surrounding medium. Fig. 1A shows a scanning electron microscopy (SEM) image of an NP ring with a
Author contributions: W.-S.C. and S.L. designed research; W.-S.C., B.A.W., and L.S.S. performed research; B.P.K., L.V., and E.R.Z. synthesized polystyrene-functionalized gold nanoparticles and assembled them into ring-like superstructures; W.-S.C. and B.A.W. analyzed data; and W.-S.C. and S.L. wrote the paper. The authors declare no conflict of interest. This article is a PNAS Direct Submission.
1

To whom correspondence should be addressed. E-mail: slink@rice.edu.

This article contains supporting information online at www.pnas.org/lookup/suppl/ doi:10.1073/pnas.1113563108/-/DCSupplemental.

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Coupled surface plasmons in one-dimensional assemblies of metal nanoparticles have attracted significant attention because strong interparticle interactions lead to large electromagnetic field enhancements that can be exploited for localizing and amplifying electromagnetic radiation in nanoscale structures. Ohmic loss (i.e., absorption by the metal), however, limits the performance of any application due to nonradiative surface plasmon relaxation. While absorption losses have been studied theoretically, they have not been quantified experimentally for strongly coupled surface plasmons. Here, we report on the ohmic loss in one-dimensional assemblies of gold nanoparticles with small interparticle separations of only a few nanometers and hence strong plasmon coupling. Both the absorption and scattering cross-sections of coupled surface plasmons were determined and compared to electrodynamic simulations. A lower absorption and higher scattering cross-section for coupled surface plasmons compared to surface plasmons of isolated nanoparticles suggest that coupled surface plasmons suffer smaller ohmic losses and therefore act as better antennas. These experimental results provide important insight for the design of plasmonic devices.

subwavelength plasmonic circuits (4, 5, 2228). For example, the propagation distances of SP polaritons are significantly reduced because of absorption losses, limiting the effectiveness of plasmonic waveguides (2228). Although a few theoretical studies have reported on absorption losses of SPs (2224, 28), quantitative experimental studies are urgently needed. In particular, a deeper understanding of the field enhancements and absorption losses for coupled SPs in NP assemblies is required for the rational design of improved plasmonic NP devices. The strength of near-field interactions between NPs is directly related to the red-shift of the coupled SP resonance as generally probed by scattering spectroscopy for small NP assemblies such as dimers and trimers (15, 29, 30). Higher order SP modes have also been observed for larger assemblies of closely spaced NPs (31). In addition, it has been shown that the spectral dependence of the electromagnetic field enhancement in these NP structures follows the collective scattering response (15, 32, 33). Because significantly larger electromagnetic field enhancements are encountered for coupled SPs (9, 11, 15, 33), more efficient plasmonic antennas can be realized for excitation at wavelengths corresponding to coupled SPs rather than the single NP SP resonance, unless the magnitude of ohmic loss also increases and absorption losses become prohibitive. Therefore, measuring both absorption ( ABS ) and scattering cross-sections ( SCA ) for coupled SPs in closely spaced NP assemblies is necessary to understand the interplay between electromagentic field enhancement and ohmic loss. While SP absorption of a single NP has been measured by photothermal heterodyne imaging (3437), absorption of redshifted coupled SPs has not been explored in detail. In this work, we separately measured absorption and scattering of coupled SPs in individual self-assembled nanostructures. Micrometer large rings composed of polystyrene-functionalized gold NPs (31) served as quasi one-dimensional (1D) NP chains, whose structures were analyzed using electron microscopy (Fig. 1A and SI Appendix, Fig. S1). Experiments were complemented by detailed electrodynamic simulations. We found that, whereas SCA increases for coupled SPs compared to isolated NPs, ABS decreases for coupled SPs compared to the SP of the individual gold NPs.

Fig. 1. Absorption and scattering of coupled SPs in a self-assembled NP ring. (A) SEM image of a ring composed of 40-nm gold NPs. The diameter of this ring was 4.6 m. (B) Scattering spectra of the ring segment (cyan) marked by the cyan rectangle in A and a single NP (orange). The purple, red, and green dashed lines represent the excitation wavelengths of 785, 675, and 514 nm that were used for photothermal heterodyne imaging. The purple, red, and green bars illustrate the spectral bandwidths of 800 20, 700 20, and 550 20 nm that were used for wavelength selective scattering imaging. C, D, and E show the photothermal images of the NP ring with circularly polarized excitation at wavelengths of 785, 675, and 514 nm, respectively. F, G, and H are the unpolarized scattering images of the ring recorded at 800 20, 700 20, and 550 20 nm, respectively. Note that the images are not scaled to each other as they were acquired adjusting the intensity of the incident or detected light so that the signal covered the full dynamic range for each experiment.

diameter of 4.6 m. Due to the large ring diameter compared to the NP size and hence small local curvature, a segment of the ring mimics a 1D NP chain. The emergence of strongly coupled SP modes was visualized by acquiring scattering spectra for approximately 500-nm-long segments along the NP ring circumference. The length of the ring segment was determined by the size of a pinhole placed in the imaging plane of a home-built single particle microscope. Fig. 1B shows a scattering spectrum with multiple, broad peaks for the ring segment (cyan) that is marked by the cyan rectangle in Fig. 1A. The additional resonances at lower energies compared to the response of a single 40-nm gold NP (orange) result from strong near-field coupling between the NPs (19, 31). Wavelength resolved imaging was used to investigate the absorption and scattering of coupled SPs for the NP ring. Fig. 1 CE display the absorption images for the ring in Fig. 1A recorded by photothermal heterodyne imaging, which selectively measures only the absorption through heat-induced refractive index changes of the surrounding medium (3439). Excitation was performed with lasers operating at 785, 675, and 514 nm as indicated by the dashed colored lines in Fig. 1B. Heating powers were kept below the threshold for laser mediated melting of the NPs as confirmed by the absence of a change in the scattering spectrum for the same local ring segment before and after photothermal imaging (SI Appendix, Fig. S2). Dark-field scattering images (Fig. 1 FH) at corresponding wavelengths were obtained by placing 40-nm band pass filters centered at 800, 700, and 550 nm in front of the avalanche photodiode. Excitations with 514 and 550 nm for absorption and scattering, respectively, are also resonant with the SP mode of the constituent 40-nm gold NPs (Fig. 1B) in addition to higher order coupled SP modes. On the other hand, at the two longer wavelengths only coupled SPs of the NP ring were excited as confirmed by measuring absorption images of single NPs with 785 and 675 nm
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(SI Appendix, Fig. S3). The coupled SP modes are more sensitive to the local arrangement of the NPs and several hot spots with large intensities that do not scale with the number of NPs per area are present in both absorption (Fig. 1 C and D) and scattering (Fig. 1 F and G) images. This result is characteristic of nonuniform electromagnetic field enhancements in strongly coupled NP clusters (40). Interestingly, at these longer wavelengths the absorption and scattering intensity distribution along the ring (i.e., the number and location of hot spots) do not correlate with each other. In contrast, at 514 nm the absorption intensity of the ring approximately scales with the number of NPs per area (SI Appendix, Figs. S4 and S5). The coupled SP absorption modes for the NP ring were further investigated by polarization sensitive imaging. For wavelengths red-shifted from the single NP SP resonance, the absorption intensities were highly polarized along the direction of the local NP alignment. Fig. 2 presents wavelength resolved and polarization sensitive absorption (left) and scattering (right) images of the NP ring for two orthogonal polarizations. At the longest wavelength (785 nm for absorption and 800 nm for scattering), both absorption and scattering intensities increased when the polarization was parallel to the local ring segment. Minimum intensities were observed for polarization directions perpendicular to the local NP alignment. A similar trend, although with less contrast, was also observed for absorption at 675 nm and scattering at 700 nm. On the other hand, the absorption and scattering images taken at the shortest wavelength did not depend on the polarization. With increasing wavelength, the polarization dependence of coupled SP modes increases for both absorption and scattering. This was quantified by recording images as a function of polarization angle in 30 increments (SI Appendix, Figs. S6 and S7). Fig. 3 A and B show the polarization dependence of the absorption intensities for 785 nm (purple), 675 nm (red), and 514 nm (green) excitation analyzed at the ring locations marked by the yellow and cyan rectangles in Fig. 1A, respectively. The corresponding data for SP scattering at 800, 700, and 550 nm is given in Fig. 3 C and D. The polarization dependence was examined by fitting the intensities I to I N1 M cos 2 where N is a normalization constant (36). The modulation depth M represents the average in plane projection of a collection of dipoles describing the system. M 1 for a single dipole or if all dipoles

Fig. 2. Polarization sensitive and wavelength dependent photothermal and scattering images of an NP ring. Photothermal images of the same ring as shown in Fig. 1A excited with horizontal (first column) and vertical (second column) polarizations, and scattering images detected with horizontal (third column) and vertical (forth column) polarizations. The excitation and detection wavelengths for absorption and scattering are displayed next to the corresponding images.

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Fig. 3. Polarization of NP ring SPs for absorption and scattering intensities along an NP ring. (A and B) Polarization dependence of the photothermal intensity of the local ring segments marked by the yellow and cyan rectangles in Fig. 1A, respectively. Purple, red, and green symbols represent excitation wavelengths of 785, 675, and 514 nm. The lines are fits and yield modulation depths of M785 0.93 and 0.76; M675 0.47 and 0.55; M514 0.06 and 0.12. (C and D) Polarization dependence of the corresponding scattering intensity for the same local ring segments. Purple, red, and green symbols represent the spectral windows of 800 20, 700 20, and 550 20 nm. The lines are fits and yield modulation depths of M800 0.82 and 0.65; M700 0.47 and 0.31; M550 0.11 and 0.05. (E and F) Histograms of the modulation depth obtained from the photothermal and scattering polarization traces, respectively. For this analysis, the ring was divided into 40 and 24 segments for the photothermal and scattering measurements, respectively. Note that the colors of the bars correspond to those of the polarization traces.

are aligned in parallel, while M 0 if the dipoles are randomly distributed (SI Appendix, Fig. S8). The phase angle gives the orientation of the average dipole moment in the sample plane with respect to a reference axis. Consistent with a parallel orientation of the coupled SP oscillations and the local NP alignment, the polarization traces for the two highlighted ring locations are 90 out of phase. Oscillation of coupled SPs parallel to the local NP alignment direction was furthermore found to be independent of the specific ring location and mostly uniform around the entire ring. The absorption and scattering images were divided into 40 and 24 areas, respectively, which was based on the resolution of the two imaging techniques. Modulation depths M and angles for each of these areas were then determined. The distributions of M values for absorption and scattering are summarized in Fig. 3 E and F. The mean modulation depths are of comparable magnitude for absorption and scattering: hM 785 i 0.75 0.21 and hM 800 i 0.66 0.11; hM 675 i 0.45 0.22 and hM 700 i 0.45 0.14; hM 514 i 0.11 0.06 and hM 550 i 0.12 0.07. The error represents the standard deviation of M. The difference for the longest wavelength is most likely due to the larger wavelength interval of 40 nm probed by scattering in combination with the wavelength dependence of M. These results demonstrate how near-field interactions between isotropically shaped NPs lead to polarized collective nonradiative modes in addition to radiative modes. Electrodynamic simulations of local ring segments were carried out to validate and further interpret the experimental results.
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Fig. 4. Experimental and simulated extinction spectra for a segment of an NP ring. (A) SEM image of a ring segment composed of 40-nm gold NPs. (B) Extinction spectra of the ring segment in A recorded with excitation polarization parallel (blue) and perpendicular (red) to the 1D NP alignment direction. (C and D) GMT calculations for the ring segment marked by the magenta square in A. The modeled NP arrangement in C was taken from the SEM image keeping the minimum surface-to-surface separation between neighboring NPs greater than 1 nm. (E and F) FEM calculations for the ring segment marked by the yellow square in A. For the FEM calculations, the NPs labeled 18 and 911 were allowed to touch and hence coupled conductively.
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Because the scattering spectrum in Fig. 1A was cut off at low energies due to the limited spectral range of the Si CCD camera, we measured broadband extinction spectra covering a range of 5001,800 nm in order to access the entire SP response of the NP ring. The SEM image in Fig. 4A shows the NP arrangement of a local ring segment. Extinction spectra recorded with linear polarization parallel and perpendicular to the local alignment of the NPs, as indicated by the blue and red arrows in Fig. 4A, are given in Fig. 4B and display a strong SP peak at 1,400 nm as well as multiple peaks between 500 and 1,000 nm. The longest wavelength SP modes are all highly polarized along the quasi 1D NP alignment. Although the relative intensities of these SP modes varied slightly from one ring area to another and for different NP rings having different diameters, all extinction spectra recorded shared similar spectral profiles (SI Appendix, Fig. S9). Using the experimental NP arrangement, we calculated polarized extinction spectra using code developed based on generalized Mie theory (GMT) (41, 42). Fig. 4C shows the arrangement of 26 NPs that were all assumed to be 40-nm spheres and spaced at least 1 nm apart. Although this presents a simplification of the actual system where the NPs are highly faceted, GMT has the advantage of being able to compute the collective optical response of a large number of NPs while including many multipoles (42). The calculated polarized extinction spectra (Fig. 4D) show multiple SP resonances for wavelengths shorter than 1,000 nm, qualitatively reproducing the experimental results except for the SP resonance at 1,400 nm, which is absent in the GMT simulations. Increasing the number of NPs in the simulation did not push the longest wavelength SP resonance beyond 1,000 nm, consistent with previous results showing that the infinite chain limit is reached for about 10 NPs (42, 43).

The longest wavelength SP resonance can be explained by conductive plasmon coupling for touching NPs. Because GMT can only solve the optical response for nontouching NPs, we used the finite element method (FEM) to simulate the NP assembly shown in Fig. 4E containing only the first 13 NPs as these FEM calculations required significantly more computer resources. The calculated extinction spectrum with longitudinal polarization in Fig. 4F shows a strong SP resonance at 1,600 nm as well as several multipolar peaks with lower intensities. For this NP arrangement conductive contact for NPs 18 and 911 was assumed. However, because of the limited resolution of SEM it was not clear which NPs were actually touching. Therefore, different NP arrangements with varying numbers of touching NPs were simulated. The geometry in Fig. 4E resulted in the best qualitative agreement between the experimental (Fig. 4B) and calculated spectra (Fig. 4F). The simulation results for other NP arrangements are given in SI Appendix, Fig. S10. Further optimization of the NP shape and assembly geometry could in principle lead to better agreement between experiment and theory, but the main conclusion here is that it is necessary to consider touching NPs to explain the longest wavelength SP mode in these NP rings, which we assign to a charge transfer plasmon resonance (4446). Because GMT matches the experimental results well for wavelengths below 1,000 nm the collective SP response in this wavelength range is assigned to mostly capacitive plasmon coupling between nontouching NPs. As all scattering and absorption measurements discussed earlier were also limited to the spectral range of 5001,000 nm, we have chosen to use GMT to interpret the experimental results. Although this approach ignores the contribution from touching NPs, important physical insight can be gained. Fig. 5A shows unpolarized absorption (magenta) and scattering (blue) spectra simulated by GMT for the ring segment marked by the cyan rectangle in Fig. 1A. The experimental scattering spectrum (cyan) recorded with unpolarized excitation is also included. The excellent agreement between the experimental and calculated spectra confirms the validity of the GMTcalculation and justifies our approach. Based on the calculated spectra, the difference in modulation depths can now be explained more quantitatively. At 785800 nm, because a combination of the SP dipole mode and the first higherorder mode was excited, the modulation depth was smaller than 1. At 675700 nm, only higher-order SP modes were excited, which resulted in a smaller modulation depth. At 514550 nm, both higher-order longitudinal as well as transverse SP modes were excited yielding the smallest modulation depth because of the orthogonal nature of these modes. Unpolarized interband transitions furthermore contributed to the reduced modulation depth at this wavelength. Strongly coupled SPs at wavelengths red-shifted from the single NP SP response have smaller ABS but larger SCA . This can be directly seen from the simulated absorption and scattering spectra in Fig. 5A but can also be further quantified experimentally. We determined ABS and SCA of the NP ring by comparing the absorption and scattering intensities for the ring and individual NPs. We measured wavelength resolved photothermal and dark-field images for the NP ring and individual gold NPs under the same conditions. To cover the three wavelength regions of interest and yield strong scattering signals, we selected NP samples with mean sizes of 96 nm, 33 63 nm, and 22 70 nm as verified separately by TEM (SI Appendix, Fig. S11). FEM calculations of ABS and SCA for these NPs were performed assuming a homogenous surrounding medium with a refractive index of 1.5 (SI Appendix, Fig. S12). Experimentally, only NPs with a peak wavelength within 10 nm of the calculated value were selected based on their scattering spectra (SI Appendix, Fig. S13). The absorption and scattering intensity ratios between the individual NPs and areas along the ring were obtained and then multiplied by the calculated ABS and SCA of the single NPs. This procedure yields ABS;ring and SCA;ring for ring areas having a size that
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Fig. 5. Absorption and scattering cross-sections of SPs in an NP ring. (A) Simulated absorption (magenta) and scattering (blue) spectra of the ring segment marked by the cyan rectangle in Fig. 1A. The experimental scattering spectrum (cyan) from Fig. 1A is also included for comparison. (BD) Histograms of ABS obtained from 40 ring segments of the photothermal images for 785, 675, and 514 nm excitation, respectively. (EG) Histograms of SCA obtained from 24 ring segments of the scattering images measured with band pass filters of 800 20, 700 20, and 550 20 nm, respectively. (H and I) Electromagnetic-field enhancements of the same NP ring segment at 785 and 514 nm, respectively.

was limited by the optical resolution. To allow for comparisons independent of the detection area ABS;ring and SCA;ring were divided by the number of NPs per integration area to give ABS and SCA , which also include normalization constants that take the different spectral observation windows into consideration. Further details regarding the calculation of ABS and SCA are discussed in the supporting information (SI Appendix, Figs. S14S16 and Tables S1S4). Fig. 5 BD shows histograms of ABS for the NP ring excited at 785, 675, and 514 nm, respectively. The median ABS is significantly lower for the SPs at 785 and 675 nm compared to the SP at 514 nm. We determined values of ABS 736 nm2 at 785 nm and
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 ABS 163 nm2 at 675 nm compared to ABS 1;048 nm2 at 514 nm. The median is used here to exclude the effect of a few hot spots that are more dominant at longer wavelengths. On the other hand, the median SCA calculated from the histograms given in Fig. 5 EG increases slightly for 800 nm ( SCA 576 nm2 ) and 700 nm ( SCA 560 nm2 ) relative to 550 nm ( SCA 521 nm2 ). The accuracy of this cross section analysis was verified by comparing the wavelength dependence of SCA;ring for the area marked by the yellow rectangle in Fig. 1A with the scattering spectrum taken at the same location (SI Appendix, Fig. S17). The very good agreement between SCA;ring and the scattering spectrum validates the procedure for the cross-section analysis. The observed trend for ABS and SCA in Fig. 5 BG also agrees well with the simulated absorption and scattering spectra in Fig. 5A. These results lead us to conclude that in NP assemblies with small interparticle distances, smaller absorption, but larger scattering occurs for strongly coupled SP resonances at lower energies compared to the single NP SP. Because the scattering intensity is directly related to the electromagnetic field enhancement (15, 32, 33), the larger SCA at red-shifted wavelengths should make coupled SPs better antennas. A larger electromagentic field enhancement at 785 nm compared to 514 nm was furthermore confirmed by calculating the field distributions (Fig. 5 H and I) using GMT for the local ring segment corresponding to the spectra in Fig. 5A. Small interparticle distances in assemblies of many NPs as investigated here in self-assembled NP rings are important to

observe lower ABS than SCA for strongly coupled SPs. This is illustrated by GMT simulations of a simpler system of ordered linear chains with varying number of NPs. Fig. 6 shows scattering (blue) and absorption (magenta) efficiencies of NP chains with interparticle gaps of 1 nm (solid line) and 20 nm (dash line), composed of 2 (A), 3 (B), 6 (C), and 10 (D) NPs. For gaps of g 1 nm, the dipole SP resonance red-shifted from 685 nm for a dimer to 862 nm for 10 NPs, while for 20 nm gaps because of reduced plasmon coupling the spectral shift was only 20 nm, which is further illustrated in the inset of Fig. 6A for chain length of up to N 15. For both interparticle distances, the scattering efficiency of at the dipole SP resonance (superradiant mode) furthermore increases relative to the absorption efficiency with increasing number of NPs. This is shown in the inset of Fig. 6B where the ration of QSCA QABS is plotted vs. N. However, only for g 1 nm scattering becomes more dominant than absorption for the ordered linear chains in Fig. 6. The stronger scattering results from an increased dipole of the collective SP response as more NPs contribute. The interparticle distances have to be small though to allow for strong coupling. Consistent with our results, calculations of NP dimers and heptamers have shown that radiation dominates the competition between scattering and absorption at the superradiant mode (47, 48). Interband absorption near the single NP resonance also contributed to the higher absorption cross section at 514 nm. Conclusions In summary, we have measured ABS and SCA of coupled SPs in self-assembled quasi 1D structures composed of 40-nm gold NPs. Coupled absorption modes excited at longer wavelengths compared to the SP of the constituent single NPs were identified by polarization sensitive imaging and verified by electromagnetic calculations. Similar to scattering, the collective nonradiative SP modes are sensitive to the overall morphology of the NP assembly as the absorption intensities were enhanced when the polarization was parallel to the local ring segments. In addition, we found a lower ABS in combination with a higher SCA for the coupled SPs in these chemically prepared NP assemblies, implying smaller ohmic losses and larger local fields at red-shifted wavelengths, allowing one to minimize absorptive losses while maximizing electromagnetic field enhancements with coupled SPs for the design of efficient plasmonic nano-antennas. Materials and Methods
Sample Preparation. Polystyrene-functionalized gold NPs (MWPS 10;000 g mol) were synthesized following the procedure described elsewhere (18). The diameter of the gold NPs was 40 5 nm as confirmed by TEM (JEOL 1230 HCTEM operated at 80 kV). By allowing a drop of the functionalized gold NPs solution to dry on a glass slide, rings were formed at the interface between the organic solvent and water droplets that condensed from the air due to evaporative cooling of chloroform. A gold pattern was evaporated onto glass slides using an indexed copper TEM grid (Ted Pella) that had no support layer, allowing us to locate the same structures in scanning electron and optical microscopy. Dark-Field Spectroscopy. Dark-field excitation was performed in a reflected light geometry using an inverted microscope (Zeiss) with a halogen lamp as the excitation source. Scattered light was collected using a Zeiss EC EpiplanNeofluar objective (50, N:A: 0.8). After passing through a 50-m pinhole, the signal was focused onto an avalanche photodiode (Perkin Elmer). A polarizer and a band pass filter were placed in the detection path after the pinhole to measure the polarization and wavelength dependence of the scattered light. The images were created by scanning the sample using a piezo scanning stage (Physik Instrumente) connected to a surface probe microscope controller (RHK Technology). Scattering spectra were acquired with a spectrometer and a Si CCD camera (Princeton Instruments). Broadband Extinction Spectroscopy. Extinction spectra were acquired using the same microscope setup. Light from a tungsten halogen lamp (Newport) was incident from above the sample to allow for excitation at normal incidence. The transmitted light was collected by a Zeiss EC Epiplan-Neofluar
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Fig. 6. Absorption and scattering efficiency of ordered NP chains. (AD) Scattering (QSCA , blue) and absorption (QABS , magenta) efficiencies of linear chains composed of 2 (A), 3 (B), 6 (C), and 10 (D) 40-nm gold NPs. The efficiency Q is defined as the optical cross section normalized by the geometric cross-section of the total number of NPs. Spectra were calculated for gaps of g 1 nm (solid line) and g 20 nm (dashed line) between neighboring NPs. The insets in A and B show the resonance maximum and the ratio of scattering and absorption efficiencies at the dipole SP mode for gaps of 1 and 20 nm as a function of NP number, respectively. The dotted horizontal line in the inset in B, QSCA QABS 1, is given as a reference to illustrate when scattering becomes more dominant than absorption.

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objective and directed either through the same 50-m pinhole toward the Si CCD camera or focused into a 100-m diameter fiber that was connected to a spectrometer (Andor Technology SR-163) equipped with an InGaAs array detector (Andor Technology DU491A-2.2). Broadband extinction spectra were then created by combining spectra from the Si CCD camera (5001,000 nm) and the InGaAs array detector (9001,800 nm). Photothermal Heterodyne Imaging. Photothermal heterodyne imaging was performed in transmission geometry (39) using the same microscope setup. A 514-nm Ar laser (Modu-Laser) and 675-nm or 785-nm diode lasers (Power Technology) were used as the heating beams. The polarization of the heating beams was controlled using half and quarter waveplates. A 633-nm He-Ne laser (JSD Uniphase) was employed as the probe beam. Each laser was focused independently to ensure best overlap at the focus between heating and probe beams for optimum resolution. The intensity of the heating beam was modulated at 400 kHz with an acousto-optic modulator (IntraAction). The laser beams were focused on the sample with a Zeiss Fluar objective (100, N:A: 1.3). The transmitted probe beam was collected by a Zeiss EC Epiplan-Neofluar objective (50, N:A: 0.8). The heating beam was rejected by a 633-nm band pass filter (Thorlabs). The photothermal signal was detected by an avalanche photodiode module (Hamamatsu) and fed into a lock-in amplifier (Princeton Applied Research), which was connected to the same surface probe microscope controller. Photothermal images were acquired by scanning the sample.
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Electrodynamics Simulations. GMT calculations were performed using a code that we have developed for modeling individual and multiple spherical metal NPs (42). For a single sphere, the electrodynamic solution for the optical crosssections is the well-known Mie theory (49) in which the scattered and incident fields are represented as a complete expansion of vector spherical harmonics with appropriate weighting coefficients. By extending this solution to N NPs, whereby the incoming scattered fields from neighboring NPs act as further excitations, the scattering coefficients for each of the N NPs are solved, yielding analytical solutions for the electrodynamic fields and optical cross-sections. FEM calculations were carried out using the commercially available software COMSOL Multiphysics, which can simulate arbitrary NP geometries including overlapping spheres that mimic the conductive overlap of neighboring NPs. All calculations were carried using tabulated values for the complex dielectric response of gold (50) and an effective dielectric medium of 1.5. ACKNOWLEDGMENTS. S.L. acknowledges financial support by the Robert A. Welch Foundation (Grant C-1664), National Science Foundation (NSF) (CHE-0955286), Office of Naval Research (N00014-10-1-0989), and 3M for a Nontenured Faculty Grant. E.R.Z. acknowledges financial support by NSF (DMR-0547399, DMR-1105878) and the Robert A. Welch Foundation (C-1703). W.S.C. thanks the Richard E. Smalley Institute for a Peter and Ruth Nicholas fellowship and L.S.S. thanks the NSF Integrated Graduate Education and Research Traineeship Nanophotonics fellowship program.
28. Seidel J, Grafstrm S, Eng L (2005) Stimulated emission of surface plasmons at the interface between a silver film and an optically pumped dye solution. Phys Rev Lett 94:117401. 29. Sonnichsen C, Reinhard BM, Liphardt J, Alivisatos AP (2005) A molecular ruler based on plasmon coupling of single gold and silver nanoparticles. Nature Biotechnol 23:741745. 30. Wustholz KL, et al. (2010) Structure-activity relationships in gold nanoparticle dimers and trimers for surface-enhanced raman spectroscopy. J Am Chem Soc 132:1090310910. 31. Chang WS, et al. (2009) One-dimensional coupling of gold nanoparticle plasmons in self-assembled ring superstructures. Nano Lett 9:11521157. 32. Ross BM, Lee LP (2009) Comparison of near- and far-field measures for plasmon resonance of metallic nanoparticles. Opt Lett 34:896898. 33. Yan B, Boriskina SV, Reinhard BM (2011) Optimizing gold nanoparticle cluster configurations (n < 7) for array applications. J Phys Chem C 115:45784583. 34. Berciaud S, Cognet L, Blab GA, Lounis B (2004) Photothermal heterodyne imaging of individual nonfluorescent nanoclusters and nanocrystals. Phys Rev Lett 93:257402. 35. Boyer D, Tamarat P, Maali A, Lounis B, Orrit M (2002) Photothermal imaging of nanometer-sized metal particles among scatterers. Science 297:11601163. 36. Chang WS, Ha JW, Slaughter LS, Link S (2010) Plasmonic nanorod absorbers as orientation sensors. Proc Natl Acad Sci USA 107:27812786. 37. Tcherniak A, Ha JW, Dominguez-Medina S, Slaughter LS, Link S (2010) Probing a century old prediction one plasmonic particle at a time. Nano Lett 10:13981404. 38. Gaiduk A, Ruijgrok PV, Yorulmaz M, Orrit M (2010) Detection limits in photothermal microscopy. Chem Sci 1:343350. 39. Giblin J, Syed M, Banning MT, Kuno M, Hartland G (2010) Experimental determination of single cdse nanowire absorption cross sections through photothermal imaging. ACS Nano 4:358364. 40. Shimada T, Imura K, Hossain MK, Okamoto H, Kitajima M (2008) Near-field study on correlation of localized electric field and nanostructures in monolayer assembly of gold nanoparticles. J Phys Chem C 112:40334035. 41. Gerardy JM, Ausloos M (1982) Absorption spectrum of clusters of spheres from the general solution of Maxwells equations. II. Optical properties of aggregated metal spheres. Phys Rev B Condens Matter Mater Phys 25:42044229. 42. Willingham B, Link S (2011) Energy transport in metal nanoparticle chains via sub-radiant plasmon modes. Opt Express 19:64506461. 43. Citrin DS (2005) Plasmon polaritons in finite-length meta-nanoparticle chains: the role of chain length unravelled. Nano Lett 5:985989. 44. Perez-Gonzalez O, et al. (2010) Optical spectroscopy of conductive junctions in plasmonic cavities. Nano Lett 10:30903095. 45. Romero I, Aizpurua J, Bryant GW, Garca De Abajo FJ (2006) Plasmons in nearly touching metallic nanoparticles: singular response in the limit of touching dimers. Opt Express 14:99889999. 46. Slaughter LS, Wu Y, Willingham BA, Nordlander P, Link S (2010) Effects of symmetry breaking and conductive contact on the plasmon coupling in gold nanorod dimers. ACS Nano 4:46574666. 47. Alu A, Engheta N (2008) Hertzian plasmonic nanodimer as an efficient optical nanoantenna. Phys Rev B Condens Matter Mater Phys 78:195111. 48. Mirin NA, Bao K, Nordlander P (2009) Fano resonances in plasmonic nanoparticle aggregates. J Phys Chem A 113:40284034. 49. Mie G (1908) Beitrge zur Optik trber Medien, speziell kolloidaler Metallsungen. Ann Phys 25:377445. 50. Johnson PB, Christy RW (1972) Optical constants of the noble metals. Phys Rev B Condens Matter Mater Phys 6:43704379.

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Chang et al.

Supplementary Information

Low absorption losses of strongly coupled surface plasmons in nanoparticle assemblies

Wei-Shun Changa, Britain A. Willinghama, Liane S. Slaughtera, Bishnu P. Khanala, Leonid Vigdermana, Eugene R. Zubareva, and Stephan Linka,b,1

Department of Chemistry, bDepartment of Electrical and Computer Engineering

Laboratory for Nanophotonics, Rice University, Houston, TX, 77005

To whom correspondence should be addressed. E-mail: slink@rice.edu

CONTENTS:
Figure S1 Figure S2 Figure S3 Comparison of photothermal intensities of isolated NPs and NP ring at 514 nm Figure S4 Figure S5 Figure S6 Figure S7 Figure S8 Figure S9 Figure S10 Calculation of SCA for the NP ring Figure S11 Figure S12 Figure S13 Figure S14 Table S1 Table S2 Figure S15

Page
4 5 5 6 7 7 8 9 9 10 11 11 12 13 14 15 15 16 17

Calculation of ABS for the NP ring Figure S16 Table S3 Table S4 Figure S17 References

17 18 18 19 20 20

Fig. S1 SEM (left) and scattering (right) images of an array of NP rings. The optical image was taken for a smaller area in order to clearly show the structure of the rings given the lower resolution. Arrays of NP rings were fabricated by first patterning arrays of circular hydrophilic areas with a hydrophobic background through the use of microcontact printing (1). A silicon wafer master was coated with photoresist and patterned on a Heidelberg DWL66 Laser Writer. A polydimethylsiloxane (PDMS) stamp was then cast from this master by pouring over it a mixture (10:1 by mass) of PDMS pre-polymer (Sylgard 184, Dow Corning) and curing agent, degassing the mixture, and heating at 70 C for 1 hour. Hydrophilic regions were then patterned onto a gold-coated glass slide by stamping of a 2 mM solution of 16-mercaptohexadecanoic acid in ethanol, followed by dipping into a 2 mM solution of hexadecanethiol in ethanol to form the hydrophobic background, and then rinsing with ethanol. The substrate was cooled to 5-10 oC and briefly exposed to moist air. The condensation of water occurred almost exclusively on the hydrophilic sites and created a periodic array of near monodisperse water droplets. Finally, a methylene chloride solution of polystyrene-functionalized nanoparticles was cast onto the substrate leading to the formation of a periodic array of NP rings after drying.

Fig. S2 Scattering spectra of the ring segment before (cyan) and after (orange) photothermal imaging to show that the heating and probe laser beams did not melt the NPs and alter the NP ring structure.

Figure S3. Wavelength dependent absorption of single gold NPs and a NP trimer. Because of the high sensitivity of photothermal heterodyne imaging, excitation of the long wavelength tail of the single NP resonance at 785 and 675 nm can be ruled out. Correlated SEM (A) and photothermal images recorded with 514 (B), 675 (C), and 785 (D) nm excitation were collected for single NPs and a trimer. At 514 nm both the trimer and the single NPs were visible, while at 675 nm and 785 nm only the trimer was observed. The white circles in (C) and (D) indicate the position of the single NPs. If the absorption intensities at 675 and 785 nm scaled linearly with number of NPs, then based on the signal to noise ratio and background levels in (C) and (D), the individual NPs would be visible as well. This is furthermore consistent with the observation that the scattering intensity of 40 nm NPs at 785 and 675 nm is zero (Fig. 1B) and that calculations predict very similar spectral profiles for absorption and scattering of NPs in this size range. Therefore, these results indicate that the absorption images of the ring for excitation at 785 and 675 nm are due to coupled SPs.

Comparison of photothermal intensities of isolated NPs and NP ring at 514 nm

The photothermal intensities of single isolated NPs and NPs in the ring were compared to show that at 514 nm the absorption intensity of the ring approximately scales with the number of NPs per area. The same 40 nm NPs that were used to assemble the NP ring were drop-casted on a glass slide followed by spin-casting a polyvinyl alcohol (PVA) film to ensure a homogenous sounding medium. Single NPs were identified by SEM. The heating and probe wavelengths for the photothermal measurements were 514 and 633 nm, respectively. For single NPs, the excitation power was 500 W. The excitation power for the NP ring was 50 W to avoid saturating the signal. The probe power was 800 W for both measurements. Fig. S4A shows a photothermal image of 40 nm NPs with 514 nm excitation. The intensities were integrated for 390 x 390 nm2 areas indicated by the white boxes, which was based on the optical resolution of the photothermal images. Fig. S4B shows a photothermal image of the NP ring with 514 nm excitation. The intensities were integrated for the same areas of 390 x 390 nm2 as shown again by the white boxes. To compare the intensity per particle of single isolated NPs and individual NPs in the ring assembly, the intensities of the different ring segments were normalized by the number of NPs contained in each of the white boxes and then scaled to an excitation power of 500 W. The number of NPs was obtained by overlaying the photothermal and SEM images.

Fig. S5 displays the power dependence of the photothermal intensity for 40 nm NPs with 514 nm excitation. The red line is a linear regression. The photothermal intensity scales linearly with the excitation power which is consistent with previous results(2) and therefore justifies the linear scaling factor used for the intensity comparison.

Fig. S4 Photothermal intensity of NPs with 514 nm excitation. (A), (B) photothermal images (6.7 x 6.7 m2) of 40 nm NPs and the NP ring for 514 nm excitation, respectively. (C) histogram of photothermal intensity of single isolated 40 nm NPs with excitation power of 500 W. (D) histogram of photothermal intensity of 40 nm NPs in the ring with excitation power of 50 W. The intensities were normalized by the number of NPs per excitation volume and scaled to the excitation power of 500 W.

Fig. S5 Power dependence of the photothermal intensity for 40 nm NPs with 514 nm excitation. The error bar represents the standard deviation of the intensity from several NPs. The red line is a linear regression. Figs S4C and S4D show the photothermal intensity histograms of single isolated NPs and single NPs in the ring assembly, respectively. The intensity distributions are comparable. The distribution of isolated NPs is slightly narrower than that of the NPs in the ring. However, several isolated NPs show higher intensities due to size inhomogeneity because larger triangular 7

NPs were also present as verified by correlated SEM imaging. The intensity histogram of single NPs in the ring assembly is broader, but the maximum intensity is not as large as those of the larger triangular NPs. Because the intensity of the NPs in the ring was normalized by the number of NPs for each integration area, the contribution from larger triangular NPs is averaged with the intensities of spherical NPs. This effect appears to lead to an apparent higher intensity per NP for some areas and hence results in the broader intensity histogram observed for the NPs in the ring assembly. Therefore, the intensities of single isolated NPs and NPs in the ring are comparable for 514 nm excitation.

Dark-field scattering is significantly less sensitive, making the same comparison to individual 40 nm NPs more difficult. However, based on the similar intensity distributions for absorption and scattering, as shown in Figs. 1E and 1H, the same conclusion should also apply for scattering.

Fig. S6 Polarized photothermal images of the NP ring for 785 nm excitation. The arrows represent the direction of excitation polarization. 8

Fig. S7 Polarized scattering images of the NP ring recorded for a spectral window of 800 20 nm. The arrows represent the direction of detection polarization.

Fig. S8 Polarization dependence of the photothermal intensity for a single spherical NP (40 nm) with 514 nm excitation (black circle), a single nanorod (22 x 70 nm) with 785 nm excitation (purple), and a single nanorod (25 x 75 nm) with 675 nm excitation (blue). The lines show fits of the data points to I ( ) = N (1 + M cos 2( )) . The recovered modulation depth M was 0.08 for the almost spherical NP consistent with an isotropic SP oscillation. In contrast, the modulation depths M for the 22 x 70 nm and 25 x 75 nm nanorods were 0.96 and 1.02, respectively. This confirms our ability to measure by polarization sensitive photothermal imaging a maximum modulation depth of unity as expected for the longitudinal dipole mode of a nanorod.

Fig S9 Unpolarized extinction spectra of local segments for different NP rings. The diameters of the rings were 4.1(top), 4.6 (middle) and 5.6 (bottom) m. The fact that the maxima of the different SP modes did not change significantly for different ring diameters confirms that the observed optical response originated from local NP segments and were not due to modes delocalized over the entire ring. In addition, independent of the ring and the local segment all spectra show SP resonances beyond 1000 nm that were assigned to SP coupling between touching NPs.

10

Fig. S10 FEM calculations of a local ring segment considering conductive coupling between neighboring NPs. The NP geometry is given in (A) and (C) and the corresponding extinction spectra are shown in (B) and (D). The excitation polarization was parallel to the long axis of the NP arragment. In (A), two groups of NPs were touching (NPs #1, 2, and NPs #6, 7). In (C), three groups of NPs were touching (NPs #1, 2, NPs #3, 4, 5, and NPs #6, 7).

Calculation of SCA for the NP ring

The scattering cross section SCA for a ring of NPs was calculated by obtaining the ratio of the scattering intensities from the NP ring (ISCA,Ring) and a single NP (ISCA,NP) and then multiplying this ratio by the theoretical SCA,NP of a single NP, as given in eq. S1.

SCA, ring = SCA, NP

I SCA, ring I SCA, NP

(S1)

SCA,NP was calculated by solving Maxwells equations for a known size of the NP and the dielectric constants of the metal and surrounding medium. To obtain efficient scattering intensities for single NPs at 800, 700, and 550 nm, we selected NPs with average sizes of 22 x 70 nm, 33 x 63 nm, and 96 nm which were first characterized by TEM (Fig. S11A-C). The size distributions of each sample were 22 4 x 70 11 nm, 33 5 x 63 12 nm and 96 7 nm (Fig. 11D), respectively. The error corresponds to the standard deviation of the NP size. The scattering

11

spectra of the NPs were calculated by FEM using the software COMSOL Multiphysics assuming the average size for each NP sample and a homogenous embedding medium with a refractive index of 1.5 (Fig. S12A).

Fig. S11 TEM images of 96 nm (A), 33 x 63 nm (B), and 22 x 70 nm (C) NPs. The scale bars represent 100 nm for all images. (D) size distribution of the three NP samples.

12

Fig. S12 Calculated scattering and absorption cross sections of NPs. Calculated scattering (A) and absorption (B) spectra of 96 nm (green), 33 x 63 nm (red) and 22 x 70 nm (purple) NPs using the software COMSOL Multiphysics. The refractive index of the medium was chosen to be 1.5. The green, red, and purple bars in (A) mark the detection wavelengths of 550 20, 700 20, and 800 20 nm, respectively. The green, red, and purple lines in (B) mark the excitation wavelengths of 514, 675, and 785 nm, respectively.
In order to measure the scattering intensities of the single NPs, we drop-cast the NP solution on a pre-cleaned glass slide, which was followed by spin-casting a thin layer of PVA film to ensure a homogeneous surrounding medium with a refractive index of 1.5. The scattering spectra of the single NPs were measured by dark-field microscopy and fit to a Lorentzian function as expected for single NPs (Fig. S13). Only NPs with a peak wavelength within 10 nm of the predicted value based on the mean size of the experimental distribution (Fig. S12A) were selected. About 20 NPs of each sample were chosen following this procedure. The scattering intensities of the three NP samples with average sizes of 22 x 70, 33 x 63, and 96 nm were then measured by dark-field microscopy using bandpass filters of 800 20, 700 20, and 550 20 nm. Fig. S14A shows a scattering image of 96 nm NPs recorded with a bandpass filter

13

of 550 20 nm. The intensities of the selected NPs were integrated over a 850 x 850 nm2 area, which was the resolution for the scattering image and is represented by the white boxes in Fig. S14A. The 96 nm NPs were chosen because the scattering intensity of individual 40 nm NPs was too low to yield reliable results. The same procedure was performed for the 22 x70 and 33 x 63 nm NPs using bandpass filters of 800 20 and 700 20 nm, respectively. In this way, we determined the measured scattering intensities (ISCA,NP) for each sample.

Fig. S13 Scattering spectra of single NPs. Representative spectra are shown for NPs taken from the samples with average sizes of 22 x 70 (A), 33 x 63 (B), and 96 nm (C). The black lines are fits to a Lorentzian function, which is the expected line shape for single NPs.

14

Fig. S14 Calculation of SCA for a NP ring. (A), (B) Scattering images (6.7 x 6.7 m2) of 96 nm NPs and the NP ring recorded with a 550 20 nm bandpass filter, respectively. The white boxes (850 x 850 nm2 each) represent the integration areas used for calculating the scattering intensity. (C) Histogram of integrated scattering intensities for the NP ring, where the integrated area corresponds to the size of the white boxes in (B). (D) Histogram of SCA,ring for the NP ring calculated using eq. S1.

The calculated SCA,NP of the 22 x 70, 33 x 63 and 96 nm NPs were obtained by integrating the simulated scattering spectra for the spectral windows of 800 20, 700 20, and 550 20 nm and then normalized by the band width of the filter (40 nm), respectively. In Table S1 the scattering intensities and SCA,NP for each NP sample are given.

Table S1: Summary of the scattering intensity and SCA for individual NPs (error is the standard deviation) Sample (detection window) 96 nm (550 20 nm) 33 x 63 nm (700 20 nm) 22 x 70 nm (800 20 nm) ISCA,NP (MHz) 7.4 0.7 1.7 0.9 2.6 1.5 SCA,NP (nm2) 2.1 x 104 1.5 x 103 4.6 x 103

The scattering intensities of the NP ring were acquired with bandpass filters of 800 20, 700 20, and 550 20 nm. Note that the scattering images of the NPs and the NP ring were measured side-by-side for each wavelength to ensure the same experimental conditions. The

15

intensities of the ring segments (ISCA,ring) were also acquired by integrating areas of 850 x 850 nm2 along the ring to compare to the single NPs. Fig. S14B shows the scattering image of the NP ring taken with a bandpass filter for 550 20 nm. Each white box represents the integration area used for the intensity calculation. The ring was divided into 24 segments according to the experimental resolution. Fig. S14C shows the histogram of the scattering intensities of these 24 segments. Values for SCA,ring of the ring were calculated using eq. S1. Table S2 shows the mean scattering intensity and SCA,ring of the24 ring segments for wavelengths of 800 20, 700 20, and 550 20 nm.

Table S2: Summary of the mean scattering intensity, SCA,ring, and SCA for the 24 ring segments (error is the standard deviation) Detection window 550 20 nm 700 20 nm
800 20 nm

ISCA,ring (MHz) 7.9 2.0 29.0 8.3

12.8 4.8

SCA,ring (nm2) (2.2 0.6) x 104 (2.5 0.7) x 104

(2.3 0.8)x 104

SCA (nm2) 560 128 656 177 608 247

Fig. S14D displays the SCA,ringt histogram of the NP ring. The numbers of NPs for each ring segment were also acquired by overlaying Fig. S14B with the SEM image and counting the number of NPs for each white box (Fig. S15A). The normalized SCA, which represents SCA,ring per NP, was calculated by SCA,ring/N where N is the number of NPs for each ring segment. SCA at 800 20, 700 20, and 550 20 nm are also listed in Table S2.

16

Fig. S15 Scattering (A) and absorption (B) images overlaid with the SEM image allowing the determination of the average number of NPs per integration area.

Calculation of ABS for the NP ring

The calculation of ABS for the NP ring was similar to that of SCA. Photothermal images were acquired from the same NPs analyzed in the scattering experiments using circularly polarized excitation. The excitation wavelengths for the 22 x 70, 33 x 63, and 96 nm NPs were 785, 675, and 514 nm, respectively. The excitation and probe powers ranged between 8 - 54 and 99 -127 kW/cm2 for the different samples to avoid signal saturation. Fig. S16A shows a photothermal image of 96 nm NPs excited at 514 nm. Each white box corresponds to the area used to calculate the intensity, which was chosen to be 390 x 390 nm2 based on the optical resolution of the photothermal images. Photothermal images for 22 x70 and 33 x 63 nm NPs were also measured, using 785 and 675 nm excitation. The measured absorption intensities (IABS,NP) of each sample are given in Table S3. The calculated ABS,NP for these samples at 785, 675, and 514 nm using the simulated spectra in Fig. S13B are also listed in Table S3.

17

Fig. S16 Calculation of ABS for a NP ring. (A), (B) Photothermal images (6.7 x 6.7 m2) of 96 nm NPs and the NP ring for 514 nm excitation, respectively. The white boxes (390 x 390 nm2) present the integration areas used for the intensity calculation. (C) Histogram of integrated absorption intensities for the NP ring, where the integrated area corresponds to the size of the white boxes in (B). (D) Histogram of ABS,ring for the NP ring calculated using eq. S2.

Table S3: Summary of the absorption intensity and ABS for individual NPs (error is standard the deviation) Sample (excitation wavelength) 96 nm (514 nm) 33 x 63 nm (675 nm)
22 x 70 nm (785 nm)

IABS,NP (V) 9.6 4.8 14.1 6.0

3.2 1.2

ABS.NP (nm2) 1.5 x 104 4.5 x 103

9.6 x 103

The photothermal images of the NP ring were also measured with 785, 675, and 514 nm excitation and circular polarization. The photothermal images of the NP ring and NPs were again measured side-by-side for each wavelength to ensure the same experimental conditions. Fig. S16B shows the photothermal image of the NP ring with 514 nm excitation. The white boxes represent the same integration areas for calculating the experimental absorption intensity as was used for the single NPs (390 x 390 nm2). The ring was therefore divided into 40 segments. Fig.

18

S16C displays a histogram of absorption intensities (IABS,ring) for 40 ring segments. Values for ABS,ring of the NP ring were calculated using eq. S2.

ABS , ring = ABS , NP

I ABS , ring I ABS , NP

(S2)

Table S4 shows the mean absorption intensity and ABS,ring of the 40 ring segments for 514, 675, and 514 nm excitation.

Table S4: Summary of the mean absorption intensity, ABS,ring, and ABS for the 40 ring segments (error is the standard deviation) Excitation wavelength 514 nm 675 nm 785 nm IABS,ring (V) 11.0 5.3 13.4 16.8 4.6 3.4 ABS,ring (nm2) (1.7 0.8) x 104 (4.3 5.3) x 103 (1.4 1.0) x 104 ABS (nm2) 1205 570 335 544 988 830

Fig. S16D shows a histogram of ABS,ring obtained from the 40 ring segments. The number of NPs within each segment was again acquired by overlaying Fig. S16B with the SEM image and counting the number of NPs for each white box (Fig. S15B). The normalized ABS, which represents ABS,ring per NP, was calculated by ABS,ring/N where N is the number of NPs for each ring segment. The mean values of ABS for the 40 rings segments at 785, 675, and 514 nm are listed in Table S4.

Although the excitation volume contained ~ 15 NPs in the case of the NP ring, the photothermal signal is dominated by changes in the refractive index of the medium and not the NPs themselves as shown by photothermal imaging of single NPs in different media(3), justifying the analysis chosen here. In addition, the good agreement between the measured photothermal intensities and calculated values for various NP sizes further verifies the accuracy

19

of photothermal imaging in determining SP absorption regardless of the volume of the NPs probed in the excitation area(4).

Fig. S17 SCA,ring (blue) at 550, 700 and 800 nm of the ring segment marked by the yellow rectangle in Fig. 1A. The yellow line shows the scattering spectrum of the same ring segment.

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