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Macroscopic Self-Assembly and Optical Characterization of NanoparticleLigand Metamaterials

Jake Fontana,* Jawad Naciri, Ronald Rendell, and Banahalli R. Ratna

A self-assembled metamaterial exhibiting a positive near-zero index of refraction at visible wavelengths is demonstrated. The metamaterial consists of thiolene-functionalized gold nanospheres self-assembled into macroscopic, crosslinked, monolayers. By measuring the real and imaginary parts of the phase shift of light transmitted through the self-assembled lms the effective index of refraction is determined as a function of wavelength. These ndings may pave a way to simply and efciently self-assemble and optically characterize multifunctional, multilayer nanoparticleligand metamaterials.

1. Introduction
Metamaterials are a large class of engineered materials, ranging from optical devices[1] to high-strength composites.[2] Recently interest has grown in optical metamaterials where the index of refraction approaches zero.[3] In such materials the phase velocity of the electromagnetic wave becomes large (low wave number), leading to a spatially uniform phase inside the material, yet remains dynamic in time allowing for energy transport, providing unique opportunities for applications.[4] If gold nanospheres, with negative permittivity values at prescribed visible wavelengths, are assembled into sufciently high-densities the index of refraction of the metamaterial can reach positive near-zero values. These metamaterials are limited to thin materials, only a few metal layers thick, due to the signicant intrinsic losses associated with the metal constituents at optical frequencies. Traditionally, top-down lithographic techniques[5] have been used to produce the nanoscopic constituents used for optical metamaterials. These techniques are complex, time consuming, expensive, producing primarily microscopic xed materials with limited particle resolution. Alternatively bottom-up or selfassembly can be used, offering a powerful and easier route, for creating optical metamaterials and is advantageous because of the ease of synthesis, feature size, and scalability. To create such lms aqueous suspensions of colloidal gold nanoparticles can be synthesized using wet chemistry methods[6] and charge-stabilized surfactants. However, surfactants permit nanoparticle aggregation since the global energy minimum
Dr. J. Fontana, Dr. J. Naciri, Dr. R. Rendell, Dr. B. R. Ratna Naval Research Laboratory 4555 Overlook Ave, SW, Washington, D.C, 20375, USA E-mail: jake.fontana.ctr@nrl.navy.mil

DOI: 10.1002/adom.201200039

occurs when the nanoparticles are in contact. To circumvent this issue gold nanoparticles can be functionalized with thiol or amine terminated ligands bonded to the gold surface to stabilize against aggregation through entropic repulsion. However, most of these ligands are not soluble in aqueous solvents, thus requiring the nanoparticles to be phase transferred to organic solvents. Though numerous techniques have been developed over the years to phase transfer nanoparticles, it has remained challenging to efciently functionalize metallic nanoparticles without aggregation.[7] Once the nanoparticles are successfully capped with the appropriate ligand self-assembly can be utilized to create macroscopic, high-density, monolayer lms. Bigioni et al.[8] created macroscopic (mm) monolayers of dodecanethiol capped 6 nm gold nanospheres using excess ligand and rapid solvent evaporation. The technique required the nanospheres to be phase transferred prior to reaction, several hours to complete the reaction and the resultant lm could not be easily transported onto other substrates. Further, they only demonstrated the technique using a specic ligand with nanospheres. Mayya et al.[9] immobilized nanospheres at a water-toluene interface using electrostatic attraction of charged aqueous nanoparticles and transferred them onto substrates using surface tension gradients from two immiscible uids. Similarly Johnson et al.[10] suspended silver nanospheres in excess ligand and then translate the nanoparticles up the walls of the vial using surface tension gradients from two immiscible uids. The techniques required the nanoparticles to be functionalized with appropriate ligands prior to the reaction and the lms were not demonstrated to be uniform, high-density monolayers over macroscopic length scales. Such thin, high-density lms make it challenging to determine the bulk properties such as the index of refraction or more accurately for these lms an effective index of refraction. Ponizovskaya et al.[11] performed nite difference time domain simulations of close-packed monolayer lms of silver nanospheres and indicated the lms can achieve a positive nearzero refractive index at visible wavelengths. Alaeian et al.[12] performed rigorous coupled wave analysis on gold nanosphere lms retrieving the refractive index, electric permittivity and proposed the magnetic permeability can reach non-unity values for even a single monolayer lm at optical frequencies. Experimentally, Wan et al.,[13] Kooji et al.[14] and Wang et al.[15] used spectroscopic ellipsometry to determine the refractive index of highdensity gold nanosphere monolayers lms. These studies report

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large discrepancies in the refractive index that can be attributed to the sensitive nature of the nanoparticle structures,[13] demonstrating the need for additional techniques to assemble and characterize thin, high-density nanoparticle lms. In this paper we introduce a single, efcient, robust and scalable technique that combines (i) the phase transfer of nanoparticles using a water miscible organic solvent, (ii) the selfassembly of nanoparticles into macroscopic (>cm), high-density, monolayer lms using phase separation and (iii) the transport of the nanoparticle-ligand lms onto non-functionalized substrates using surface tension gradients. We optically characterized a self-assembled, crosslinked, 17 nm gold nanosphere monolayer lm by measuring the real and imaginary parts of the phase shift of light transmitted through the lms using a conoscopic Mach-Zehnder interferometer and a spectrophotometer and determine the effective optical refractive index. To the best of our knowledge these are the rst spectroscopic, real and imaginary phase shift measurements based on transmittance reported for high-density, macroscopic, nanoparticleligand monolayer lms.

2. Results and Discussion

The lms were self-assembled using three primary constituents: citrate stabilized 17 nm diameter gold nanospheres dispersed

in water, tetrahydrofuran (THF) and thiol-ligands. The chemical structure of the two ligands thiol-ene (SC6V[16]) and di-thiol (SC6S) are shown in Figure 1ab. Macroscopic, self-assembled gold nanosphere monolayer lms were produced by placing the aqueous suspended nanoparticles into a glass vial and mixing with the thiol-ligands suspended in THF and a small amount of photoinitiator. The suspension mixture was then vigorously shaken (Figure 1c). The thiol-ene and di-thiol ligands rapidly form a covalent bond to the gold nanoparticles in suspension, causing the gold nanospheres to phase transfer, becoming hydrophobic and more miscible in THF. The lower density of THF, relative to water, causes the THF to move towards the air-uid interface, carrying the phase transferred nanospheres. The nanoparticles are conned at the air-uid interface by the reduction in the free energy (Figure 1d), approximately kBT per nanoparticle, where kB is the Boltzmann constant and T is absolute temperature. In addition to mixing, shaking the vial also leads to wetting the sides of the vial with a thin lm of solution. The THF in the thin lm evaporates faster than the water, causing a surface tension gradient.[9] The uid ows from the low (bulk suspension) to high (thin lm) surface tension area carrying the nanoparticle lms up the sides of the vial with velocities as high as millimeters per second (Figure 1e). Within minutes nearly all nanoparticles are removed from the suspension (Figure 1f, movie available in the Supporting Information). The rate the

Figure 1. Self-assembly technique. (a) SC6V; 4-(5-hexenyloxy)phenyl 4-(6-mercaptohexyloxy)-benzoate. (b) SC6S; 1,6-hexanedithiol. (c) Vial containing a suspension of metallic nanoparticles, ligands, tetrahydrofuran and water. Inserted image: reaction mixture. (d) Phase separation and metallic nanoparticle lm formation. Inserted image: initial gold nanosphere lm formation. (e) Metallic nanoparticle lm transport using surface tension gradients. Inserted image: gold lms translating up the sides of the vial. (f) End of the phase transfer and transport technique. Inserted image: gold nanosphere lms attached to the sides of the vial.

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nanoparticles are removed from suspension also depends on the concentration of ligand (details in Supporting Information). If gold nanospheres suspended in water and THF are mixed together the reaction does not occur. If small quantities of ligands are added, sufciently less than the surface area of the nanoparticles, the lm does not form at the air-liquid interface or rise up the side of the vial. Once enough ligand was added to cover approximately the entire surface area of the nanoparticles lm formation was observed at the air-liquid interface and the lms would translate up the side of the vial. Adding excess ligands greatly increased the speed and nal height the lms reached on the vial surface. The excess ligand most likely lowers the surface tension in the bulk suspension, enhancing the surface tension gradients. If the THF is replaced with a similar surface tension, lower vapor pressure organic liquid such as dimethyl sulfoxide the lm assembly rate and height of the lm on the side of the vial is signicantly reduced. The nanoparticle lms can be transferred onto substrates, such as glass or silicon wafers, by placing the substrate into the vial prior to shaking. After shaking, the nanoparticle lms translate up the substrate in the same manner as the sides of the glass vial. Once the reaction is complete the thiol-ene capped nanospheres are exposed to UV-light for several seconds to initiate ligand crosslinking, via thiol-ene click chemistry[17] to create a crosslinked lm of nanoparticles. A chloroform wash of the lms did not alter the monolayer uniformity over centimetersize domains, providing evidence they are crosslinked lms. In contrast, if the lms were not exposed to UV light they were easily washed away with organic solvents (details in Supporting Information). Figure 2 shows the monolayer scale (cm) achievable with this self-assembly technique without coffee-ring effects or regions of multiple layers on a non-functionalized substrate. Figure 2a is an image of a self-assembled, crosslinked, 17 nm gold nanosphere monolayer lm on a glass substrate partially transmitting light (left side), demonstrating preservation of the plasmon resonances, uniformity, optical clarity and reecting light (right side), demonstrating a high volume fraction of nanoparticles (photograph details are in the experimental section). Figure 2b is an SEM image of self-assembled, crosslinked, SC6V-SC6S capped 17 nm gold nanosphere monolayer lm on silicon wafer substrates. In addition to the SEM images demonstrating the lms are monolayers over centimeter length scales (Figure 2b) the thickness of the lm, t, on the glass substrates was calculated from absorbance, x, measurements to be t = x/ 16 nm, corresponding to approximately one monolayer, where 3 1023 [NP/m3] is the number density and 1.3 1016 [m2/NP] is the absorption cross-section.[18] The fast Fourier transform (FFT) was calculated from the image using ImageJ, from the Fourier transform the center-to-center spacing was measured to be 21.5 0.82 nm where the uncertainty is the standard deviation between the measured values. This corresponds to a particle-particle spacing of d = 4.5 nm (Figure 2b inset). Multi-functional, multi-layered lms can be achieved using the self-assembly technique. After one monolayer lm was transferred onto a glass substrate the substrate was removed from the vial, held outside the vial for 30s and then placed back into the vial. Another monolayer lm was translated onto

Figure 2. Macroscopic gold nanoparticle monolayers. (a) gold nanosphere-crosslinked lm on a glass substrate is partially transmitting light (left side) and reecting light (right side). (b) False-color SEM image and FFT (inset) of the crosslinked 17 nm gold nanosphere lm.

the initial monolayer, creating a bilayer lm. The reproducibility and mechanisms for creating the bi-layer lms are not well understood and will be studied in future experiments. The absorbance for a SC6V-SC6S capped 30 nm gold nanosphere mono/bi-layer crosslinked lm on a glass substrate is shown in Figure 3a. The absorbance roughly doubles (discretely) in magnitude translating from the monolayer regions onto the bilayer regions. Although shifted due to particle-particle coupling, the plasmon resonances are preserved well for the crosslinked lms given the ultra high-density of nanospheres. The technique can also be used to form high-density monolayers of gold nanorods (details in Supporting Information). The technique can also be used as a simple, fast and efcient phase transfer tool to functionalize nanoparticles of different compositions, shapes and sizes with nearly 100% particle transfer and recovery, in contrast to previous work.[10] Once all the nanoparticles were functionalized and removed from the initial reaction suspension (Figure 1f) the remaining solution can be decanted and the vial dried. The nanoparticles on the side of the vial can then be quickly re-suspended in organic solvents. Figure 3b shows the normalized absorbance spectra for gold and silver nanospheres and nanorods initially suspended in water and after being phase transferred with dodecanethiol and re-suspended in chloroform.

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Figure 4. Absorbance peak shift. (a) normalized experimental absorbance data for a dilute aqueous 17 nm gold nanospheres suspension(dotted line) and a SC6V-SC6S capped 17 nm gold nanosphere crosslinked monolayer lm (solid line). (b) COMSOL Multiphysics 4.2a simulations for the absorbance peak shift vs. interparticle separation. The inset is an image generated from COMSOL Multiphysics 4.2a of the nanoparticleligand lm.

Figure 3. Absorbance spectra. (a) absorbance of monolayer and bilayer crosslinked 30 nm gold nanosphere lm. Inserted image: mono/bi-layer lm on a glass substrate (b) absorbance of aqueous and organic suspensions of various size, shape and material nanoparticles: 20 nm silver nanospheres (blue). 10 nm gold nanospheres (green). 10 nm 45 nm gold nanorods (red).

Figure 4a shows the signicant absorbance peak shift for a SC6V-SC6S capped 17 nm gold nanosphere crosslinked monolayer lm relative to a dilute water suspension of 17 nm gold nanospheres. The large non-linear absorption peak shift is usually attributed to the near eld coupling between nanoparticles.[19] Finite-element simulations were undertaken using COMSOL Multiphysics 4.2a to develop an understanding of the absorbance peak shift from the nanoparticle-ligand interactions. Figure 4b shows the absorbance peak position versus interparticle separation. SC6V-SC6S ligand shells of various thickness, with refractive index ns = 1.6 (estimated using ACD/Labs), were placed around the gold nanospheres and hexagonally packed in a unit cell on a glass substrate surrounded by air with periodic boundary conditions and probed with unpolarized light, inset Figure 4b.

From the experimental absorbance data the SC6V-SC6S capped nanosphere lm in air had an absorbance peak at = 693 nm Figure 4a), a considerable peak shift of = 174 nm from the dilute aqueous suspension. The COMSOL simulations calculate an interparticle spacing of d = 1 nm to achieve this shift, but a d = 4.5 1.6 nm spacing was measured using SEM and FFT. The expected interparticle spacing for the SC6V-SC6S capped nanospheres lm is approximately d = 34 nm (estimated using ACD/Labs). The measured value is comparable to the expected value but varies considerably from the simulation value. A possible source of uncertainty is the estimated refractive index of the ligand shell, though a refractive index of 2.8 is required in the simulations to shift the peak to 700 nm with an interparticle spacing of 4 nm which is physically unlikely.

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Figure 5. Conoscopic Mach-Zehnder interferometer. (a) Schematic for the experimental setup to measure the real phase shift of light transmitted through the gold nanosphere monolayer lms. (b) Refractive index of crosslinked 17 nm gold nanosphere monolayer lm: (left) real and (right) imaginary refractive index as a function of wavelength. The inset is the gure of merit.

system and a spectrophotometer (Figure 5a, see the Experimental Section for details). To measure the real phase shift of the nanosphere-ligand lm, relative to air, two lenses were placed into one arm of a Mach-Zehnder interferometer to focus then collimate the beam. The lm, on a glass substrate, was positioned normal to the beam near the common focus of the two lenses. If the lm is translated out of the beam, probing only the glass substrate, a symmetric concentric ring interference pattern is formed. Translating the lm halfway across the cross-section of the beam, such that half of the interference pattern probed the air-glass and the other half was lm-glass, causes the lmglass fringes to translate radially relative to the air-glass fringe positions, but remain concentric. The lm was then translated in the probe beam direction to image the lm in the far-eld on a screen and the interference pattern was recorded with a CCD camera as a function of wavelength. The exact center of the interference pattern was determined and the distances from the center to the rst order intensity maximum, for both the air-glass and lm-glass halves of the interference patterns were measured (details in Supporting Information). The difference in these measurements determined the relative real phase shift = 2x(n lm nair )/ between air and the lm as a function of wavelength where n lm,air is the real index of refraction of the lm and air, respectively, and is the free-space wavelength. To determine the imaginary phase shift the absorbance for the lm was measured and the imaginary phase is calculated lm = x/2 = 2xnlm/, where nlm is the imaginary index of refraction of the lm. The real and imaginary index of refraction was calculated by inverting the phase shift and solving for nlm; nlm = nair + /2x, nlm = lm/2x. Figure 5b shows the index of refraction for the SC6V-SC6S 17 nm gold nanosphere monolayer lm probed from = 590 680 nm. The refractive index varies from n = 0.19 + 1.45i at = 630 nm to n = 2.35 + 1.97i at = 680 nm. The error bars for n measurements represent the standard deviation between three separate data sets and for n are the uncertainty in the measurement. In Figure 5b, the refractive index remains positive, though reaching near-zero values at = 630 nm. The gure of merit is calculated FOM = |n/n| for the lm (inset in Figure 5b) and varied from 0.1 at = 640 nm to 1.4 at = 590 nm .

Wessels et al.[20] experimentally demonstrated that increasing the conjugation of the thiol-ligand red-shifted the absorbance spectra for nanosphere-ligand lms. They attributed the differences to the formation of a resonant state at the interface due to an overlapping molecular orbital and metal wave function, causing an apparent increase in nanosphere diameter. The increase in conjugation may help explain the large red-shifts observed in our lms. We determined the refractive index of the self-assembled, crosslinked, 17 nm gold nanosphere monolayer lm by measuring the real and imaginary phase shift of light transmitted through the lm. The real and imaginary parts of the phase shift were determined using a conoscopic Mach-Zehnder interferometer probed with a spectroscopic continuous-wave laser

3. Conclusion
We developed an efcient, robust and scalable self-assembly technique that can be generalized using particles of different composition, size and shape to create high-density macroscopic metamaterials. Metallic nanoparticles can be quickly phase transferred, with a variety of thiol-ligands, and re-suspended in organic solvents with nearly 100% nanoparticle transfer and recovery. The technique self-assembles macroscopic nanoparticle-ligand monolayers and transports them onto non-functionalized substrates using a single technique. We established a simple method to determine the effective optical refractive index and demonstrated positive near-zero index of refraction, at prescribed wavelengths, for self-assembled, crosslinked, 17 nm gold nanosphere monolayer lms.

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We envision that the self-assembly technique will enable the development of multi-functional, multi-layered nanoparticle-ligand structures and provide a simple and efcient route to enable the large scale production of metamaterials for applications.[21] In addition, our optical characterization technique provides a direct measurement for the real and imaginary phase shifts from the nanoparticle-ligand lm and a straightforward means to determine the effective refractive index as a function of wavelength.

and a lens expands the interference pattern onto a screen. The lm was then translated in the beam propagation direction to image the lm in the far-eld on the screen and the interference pattern was recorded with a CCD camera (Thorlabs USB2.0 CMOS camera, 12 mm EFL f/1.8 lens) as a function of wavelength.

Supporting Information
Supporting Information is available from the Wiley Online Library or from the author.

4. Experimental Section
Self-Assembly Technique: The technique consisted of freshly synthesized citrate stabilized 17 1.4 nm diameter gold nanospheres dispersed in one milliliter of water (SPI supplies; volume fraction 104), thiol-ligands; SC6V (4-(5-hexenyloxy)phenyl 4-(6-mercaptohexyloxy)benzoate;[16] used at 5 mg/mL) and SC6S (Sigma 1,6-hexanedithiol; used at 5 mg/mL) with photoinitiator (Irgacure 369 used at 1% wt) dispersed in one milliliter of tetrahydrofuran (THF). The technique is not constrained to unique ligands; dodecanethiol and undec-10-ene1-thiol were also used with no noticeable differences in the kinetics of the reaction. The constituents were then placed into a 20 ml vial and vigorously shaken. After shaking, the metallic nanoparticle lms translate up the glass substrate (1.25 25 1 mm). If capped with proper ligands the nanoparticles can be exposed to UV-light (Dymax Bluewave 200, = 280450 nm, I = 40 W/cm2) for several seconds crosslinking the nanoparticles together. The lms were washed with chloroform to remove any excess ligands and dried with N2. Transmission/Reection Image: The image in Figure 2a was taken with a Canon EOS Rebel T3i camera by placing the lm on a glass substrate onto a backlight which was then tilted until the reection from the overhead room lights covered half of the lm. SEM Measurements: Gold nanoparticles were capped with ligands, self-assembled into a monolayer, and transferred onto silicon wafer substrates (cleaned with Piranha solution; 3:1 sulfuric acid to 30% hydrogen peroxide), using the technique described above, to examine the nanoscopic lm using a scanning electron microscope, SEM (Carl Zeiss, Model 55). Absorbance Measurements: Absorbance measurements were carried out using an unpolarized white light (Mikropack DH-2000) passing normally through the lm or suspension, the transmitted light was collected with a 400 m core diameter ber optic cable connected to a photospectrometer (OceanOptics Redtide USB650). Real Phase Shift Measurements: The refractive index for the monolayer lms was determined by measuring the real and imaginary phase shift of light transmitted through the lm. The real phase shift of the lm, relative to air, was measured using a conoscopic Mach-Zehnder interferometer (Figure 5a). A Coherent I-308 CW Argon laser (vertical linear polarized) was used to pump a Coherent 59921 Dye laser, with a range of wavelengths = 580700 nm. From the dye laser the beam is split with a beamsplitter one path goes into a spectrometer (OceanOptics Redtide USB650) to measure the output wavelength. The other beam enters a spatial lter consisting of a microscope lens with a 7 mm focal length focused onto a 10 m pin hole plate to expand the beam. A lens is then used to collimate the beam. The beam enters the Mach-Zehnder interferometer and enters a 50/50 unpolarized beamspliter (BS1). A variable attenuator was placed in the upper-right arm (BS1-M2-BS2). Two lenses (L1, L2; Newport, M-10x, 0.25NA) were placed into lower-left arm (BS1-M1-BS2) of the Mach-Zehnder interferometer to focus then collimate the beam. The lm, on a glass substrate, was translated into the beam near the common focus of the two lenses. The beam then enters a planar liquid crystal cell (WP), oriented in the vertical, applying a voltage to the liquid crystal cell aligns the E7 liquid crystal in the beam propagation direction, decreasing the phase through the cell determining the sign of the interference fringe shift. Both arms are combined (BS2)

Acknowledgements
This work was supported with funding provided from the Ofce of Naval Research. J. Fontana is a NRC-NRL postdoctoral resident at the Naval Research Laboratory. J. Naciri and B. Ratna are afliated with the Center for Biomolecular Science and Engineering and R. Rendell with the Electronics Science and Technology division at the Naval Research Laboratory. J. Fontana acknowledges the National Research Council for a postdoctoral associateship and also thanks P. Palffy-Muhoray for past discussions. We thank C. Spillmann and S. Trammell for reviewing the manuscript. Received: August 16, 2012 Revised: October 23, 2012

[1] V. M. Shalaev, W. S. Cai, U. K. Chettiar, H. K. Yuan, A. K. Sarychev, V. P. Drachev, A. V. Kildishev, Optics Lett. 2005, 30, 3356. [2] P. Podsiadlo, A. K. Kaushik, E. M. Arruda, A. M. Waas, B. S. Shim, J. D. Xu, H. Nandivada, B. G. Pumplin, J. Lahann, A. Ramamoorthy, N. A. Kotov, Science 2007, 318, 80. [3] A. Alu, M. G. Silveirinha, A. Salandrino, N. Engheta, Phys. Rev. B 2007, 75. [4] S. Kocaman, M. S. Aras, P. Hsieh, J. F. McMillan, C. G. Biris, N. C. Panoiu, M. B. Yu, D. L. Kwong, A. Stein, C. W. Wong, Nat. Photonics 2011, 5, 499. [5] a) S. M. Xiao, U. K. Chettiar, A. V. Kildishev, V. P. Drachev, V. M. Shalaev, Optics Lett. 2009, 34, 3478; b) A. Sundaramurthy, P. J. Schuck, N. R. Conley, D. P. Fromm, G. S. Kino, W. E. Moerner, Nano Lett. 2006, 6, 355; c) S. R. Quake, A. Scherer, Science 2000, 290, 1536; d) S. H. Ahn, L. J. Guo, Adv. Mater. 2008, 20, 2044; e) D. Chanda, K. Shigeta, S. Gupta, T. Cain, A. Carlson, A. Mihi, A. J. Baca, G. R. Bogart, P. Braun, J. A. Rogers, Nat. Nanotechnol. 2011, 6, 402. [6] G. Frens, Nat. Phys. Sci. 1973, 241, 20. [7] R. A. Sperling, W. J. Parak, Philos. T. R. Soc. A 2010, 368, 1333. [8] T. P. Bigioni, X.-M. Lin, T. T. Nguyen, E. I. Corwin, T. A. Witten, H. M. Jaeger, Nat. Mater. 2006, 5. [9] K. S. Mayya, M. Sastry, Langmuir 1999, 15, 1902. [10] E. M. Spain, D. D. Johnson, B. Kang, J. L. Vigorita, A. Amram, J. Phys. Chem. A 2008, 112, 9318. [11] E. V. Ponizovskaya, A. M. Bratkovsky, Appl. Phys. A-Mater. 2007, 87, 175. [12] H. Alaeian, J. A. Dionne, Opt. Express 2012, 20, 15781. [13] D. H. Wan, H. L. Chen, Y. S. Lin, S. Y. Chuang, J. Shieh, S. H. Chen, ACS Nano 2009, 3, 960. [14] E. S. Kooij, H. Wormeester, E. A. M. Brouwer, E. van Vroonhoven, A. van Silfhout, B. Poelsema, Langmuir 2002, 18, 4401. [15] D. S. Wang, C. W. Lin, Optics Lett. 2007, 32, 2128. [16] J. Lub, D. J. Broer, N. vandenBroek, Liebigs Ann. Recl. 1997, 2281.

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[17] J. P. Phillips, N. M. Mackey, B. S. Confait, D. T. Heaps, X. Deng, M. L. Todd, S. Stevenson, H. Zhou, C. E. Hoyle, Chem. Mater. 2008, 20, 5240. [18] O. L. Muskens, P. Billaud, M. Broyer, N. Fatti, F. Vallee, Phys. Rev. B 2008, 78. [19] I. Romero, J. Aizpurua, G. W. Bryant, F. J. G. de Abajo, Opt. Express 2006, 14, 9988.

[20] J. M. Wessels, H. G. Nothofer, W. E. Ford, F. von Wrochem, F. Scholz, T. Vossmeyer, A. Schroedter, H. Weller, A. Yasuda, J. Am. Chem. Soc. 2004, 126, 3349. [21] a) C. D. Zangmeister, J. M. Beebe, J. Naciri, J. G. Kushinerick, R. D. van Zee, Small 2008, 4, 1143; b) S. M. Adams, S. Campione, J. D. Caldwell, F. J. Bezares, J. C. Culbertson, F. Capolino, R. Ragan, Small 2012, DOI: 10.1002/smll.201102708.

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