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Plasmonic Shaping in Gold Nanoparticle Three-Dimensional Assemblies Till Jägeler-Hoheisel, Julien Cordeiro, Olivier Lecarme, Aurélien Cuche, Christian Girard, Erik Dujardin, David Peyrade, and Arnaud Arbouet J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/jp406410k • Publication Date (Web): 24 Sep 2013 Downloaded from http://pubs.acs.org on September 29, 2013

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The Journal of Physical Chemistry

Plasmonic Shaping in Gold Nanoparticle Three–Dimensional Assemblies Till Jägeler-Hoheisel,†,‡ Julien Cordeiro,¶ Olivier Lecarme,¶ Aurélien Cuche,† Christian Girard,† Erik Dujardin,† David Peyrade,∗,¶ and Arnaud Arbouet∗,† CEMES, UPR 8011, CNRS-Université de Toulouse, 29 rue Jeanne Marvig, BP 94347, F-31055 Toulouse, France, Institut für angewandte Photophysik, Technische Universitiät Dresden, George-Bähr-str.1,01069 Dresden, Germany, and Laboratoire des Technologies de la Microélectronique Grenoble, F-38054, France E-mail: [email protected]; [email protected]

∗ To

whom correspondence should be addressed UPR 8011, CNRS-Université de Toulouse, 29 rue Jeanne Marvig, BP 94347, F-31055 Toulouse, France ‡ Institut für angewandte Photophysik, Technische Universitiät Dresden, George-Bähr-str.1,01069 Dresden, Germany ¶ Laboratoire des Technologies de la Microélectronique Grenoble, F-38054, France † CEMES,

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Abstract When a large number of similar gold particles are organized into complex architectures, the dipolar plasmon spectrum of the individual plasmonic entities gives rise to a broader, red– shifted feature centered around 750 nm. In this work, we show that super-structures fabricated using Convective Assisted Capillary Force Assembly method (CA-CFA) and excited at that wavelength display a subwavelength patterning of their optical field intensity that results from the self-consistent coupling between the colloidal nanoparticles. First, we demonstrate the fabrication of shape–controlled three–dimensional assemblies of metallic nanocrystals using the CA-CFA method . In a second step, the absorption band resulting from the mutual coupling between the metallic building blocks is exploited to excite a coupled plasmon mode and map the Two-Photon Luminescence (TPL) by scanning a tightly focused light beam. Highly resolved TPL images show that the morphology of the plasmonic particle assemblies has a strong impact on their optical response. A model based on a rigorous optical gaussian beam implementation inside a generalized propagator derived from a three-dimensional Green dyadic function accurately reproduces the TPL maps revealing the influence of interparticle separation and thus coupling between the individual particles. Finally, we show that the spatial distribution of the electric field intensity can be controlled by tuning the linear polarization of the optical excitation.

Keywords : Colloids, 3D–assembly, micro contact printing, self–assembled plasmonics, two– photon luminescence, gold nanoparticles.

Introduction During the past two decades, plasmonics has moved towards technological applications ranging from information processing devices to biological sensors. 1–3 Simultaneously, research in this field has allowed to considerably improve the understanding of interactions between photons and surface plasmons (SP) at the nanometer scale. 4 In particular, the intensive investigation of the localized SP resonances 5–10 of individual or coupled structures has highlighted a new class of fasci2 ACS Paragon Plus Environment

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nating phenomena occurring in ultra–small geometry (dark modes, 8 Fano resonances, 11–14 spontaneous emission rate enhancement, 15 modal quality factor, 16 modal phase change mapping, 17 local heating. 18–20 ). Generally, the SP modal characteristics are investigated on bulk objects fabricated by e–beam lithography 21–23 or by colloidal chemistry 5,10,24,25 but recent studies 26–32 have shown the interest to work with three dimensional (3D) assembled metallic objects structured at the nanometer scale because of the possibility of sculpting their optical properties in three dimensions. 33–35 These advances include DNA–guided crystallization of colloidal nanoparticles producing highly regular interparticle spacings, 33,34,36 fabrication of complex and extended networks of interconnected chains of nanoparticles by spontaneous self–assembly, 30,31 and more recently substrate–supported 3D plasmonic multimer architectures composed of a small number of gold particles. 35 In this work, we present a fabrication method based on the Convective Assisted Capillary Force Assembly (CA-CFA) of a large number of colloidal plasmonic particles into shape–controlled 3D metallic super-structures with unique optical properties. 37–41 This technique consists in fabricating micron–sized assemblies of arbitrary footprint (e.g. square, four branched–star, triangle or disk) from a mono–disperse suspension of colloidal gold particles. First, a description of the vertical assembly process of assembled superstructures of arbitrary shapes is presented. Then, their peculiar optical properties are investigated both experimentally and theoretically. In particular, we excite a long range coupled SP mode arising from the collective response of the electromagnetically coupled localized plasmonic particles by tuning the laser excitation to the infrared and record the resulting TPL signal. 25,42–46 The highly resolved TPL maps evidence the strong influence of the structure morphology and show that the spatial distribution of the optical field intensity can be controlled by the linear polarization of the optical excitation. These results are analyzed using a model based on the three–dimensional Green Dyadic Method (3D-GDM). 47,50 Our numerical simulations confirm that delocalized plasmon modes observed over the entire templated aggregate result from high order dipolar plasmon couplings inside the colloidal assemblies and from the volume shaping of the superstructure.



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Three–dimensional assembly processing

Figure 1: (color online) Left : 3D structure fabrication process. (a) Preparation of the assembly substrate by e–beam lithography of a PMMA substrate layer deposited on an ITO-coated glass slide. (b) CA-CFA of the colloidal suspension by controlled evaporation in a microfluidic cell. (c) Assembled sample after total evaporation. (d) Removal of the PMMA resist by immersion in an acetone bath. (e) Resulting 3D metallic structures made of colloidal gold particles. Right: Four SEM images of nanoparticle architecture assemblies realized with 100 nm ± 5 nm gold particles. The typical height of the super-structures is 250 (A), 490 (C and D) and 950 nm (B). In this section, we describe the fabrication of shape-controlled 3D metallic structures using the novel Convective Assisted Capillary Force Assembly (CA-CFA) method. 40,41 The initial step consists in preparing the substrate on which the nanoparticles (NPs) are assembled (Figure 1a). This substrate is a glass slide covered with a thin layer of indium tin oxide (ITO). Patterns are created by electron-beam lithography in a spin-coated polymethylmethacrylate (PMMA) layer of controlled thickness. Then, 100-nm diameter gold colloids are assembled on the substrate by CA–CFA (Figure 1b) creating ordered arrays of individual objects and large scale area assemblies. 40,41 CA-CFA relies on the controlled evaporation of a colloidal suspension deposited on top of a microstructured substrate leading to a deterministic positioning of NPs on the surface. The environmental parameters such as temperature and humidity are controlled by confining the colloidal droplet in 4 ACS Paragon Plus Environment

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a poly(dimethylsiloxane) (PDMS) microfluidic cell. As a consequence, the evaporation rate is controlled, and two main effects appear and can be tuned. First, the hydrodynamic drag force Fd confines the NPs at the air-liquid-solid contact line. In a second step, the NPs are pushed into the cavities by the capillary forces Fc . Once the assembly is completed (Figure 1c), the PMMA layer is lifted-off in acetone (Figure 1d), leaving the assembled nanoparticle mesas intact on the sample (Figure 1e). The PMMA thickness and the CA-CFA parameters were adjusted to yield close-packed assemblies with different volumes ranging from 0.03 to 1.57 µ m3 . In addition various shapes were chosen to study the effect of corner sharpness (circle: no angle; hexagon: 120◦ ; square: 90◦ ; triangle: 60◦ , and star: 30◦ ). As an example, in Figure 1 we present a selection of four 3D super-structures of controlled height obtained by the CA-CFA method. In the following we will focus on 490 nm thick structures.

Optical spectroscopy and TPL imaging The optical response of the 3D plasmonic particle assemblies is first investigated by dark-field scattering spectroscopy. As shown in Figure 2 a), a broad plasmon band centered around 750 nm in the far-field optical spectra emerges from the 3D micrometer-scale nanoparticle super-structures. This spectral signature is reminiscent of similar features observed in the absorption spectra of crosslinked colloidal particle chains. 28,29 Indeed, Plasmonic Nanoparticle Networks (PNN) not only display the expected transverse plasmon mode (around 520 nm) associated with the individual particles but also a lower energy mode (located around 700 nm) resulting from the self-consistent couplings between the metallic particles. 29 In these architectures, the position of the infrared surface plasmon resonance related to interparticle coupling was shown to be weakly dependent on the number of particles in the chain or even on the topology (branched or linear) of the entire particle network. 28 The present work further generalizes this loose chain network superstructure to more compact 3D particle assemblies, in which the SP delocalized modes can be tailored by CA-CFA. Similarly to the PNN case, Figure 2 a) shows that the wavelength of the SP resonance evidenced



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Figure 2: a) (color online) Typical far–field scattering spectra generated by large arrays of identical superstructures. They display large (750 nm) scattering bands revealing strong optical coupling inside the close-packed arrangement of the gold nanoparticles. Six different profiles have been considered: Square, disk, cross, triangle, star, and hexagone. b) Scattering efficiency at 750 nm normalized to the super-structure geometrical cross-section. in the infrared is not significantly affected by the morphology of the mesa. On the contrary, the intensity of the scattered light shows large variations depending on the in-plane shape pattern of the super-structure. The ratio of the scattered intensity to the pattern area can be considered as constant as shown in Figure 2 b). This suggests that the variations in scattering efficiency are mainly due to the difference in geometrical cross-section. In the following, we investigate the modal characteristics of this infrared SP resonance. We use TPL microscopy to reveal the optical field intensity distribution in super-structures of different shapes and we perform numerical simulations to address the role of structure morphology and electromagnetic coupling strength. Two-Photon Luminescence (TPL) in gold arises from two-photon induced interband transitions of electrons from the d-band to the conduction band followed by their radiative recombination.


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TPL of gold films is generally very weak due to the many competing non-radiative relaxation pathways available in the metal. However, it can be significantly enhanced on nanostructures supporting localized SP resonances. In the latter case, TPL microscopy can yield complementary information about these optical excitations such as spectroscopic characterization, 43 diffraction-limited plasmon mode maps 44 or quantitative field enhancement measurements. 48 In a recent report, 25 we

Figure 3: (color online) Schematic view of the TPL experimental setup. have shown that TPL maps recorded on individual crystalline triangular gold nanoprisms exhibit a highly localized intensity distribution, which is dependent on both incident polarization and wavelength and is ultimately connected to the SP density of states (SP-DOS) inside the metallic particle. A similar experimental setup is used in the present work (Figure 3). It consists in a custom–built optical microscope illuminated with a commercial Ti:Sapphire femtosecond laser delivering 120 fs linearly polarized near–infrared pulses tunable between 680 and 1080 nm. The excitation beam, the polarization of which is controlled by a λ /2 plate, is tightly focused in a 300 nm fwhm excitation spot with a maximal power of 100-300 µ W at the back aperture of the objective. The TPL intensity is collected in epi–collection geometry. The sample is mounted on a XY piezostage and raster scanned in the excitation focal spot. The arrangement of the superstructures in a matrix together with position marks on the substrate allows to unambiguously match the TPL images with the SEM micrographs. Figures 4a-c show the SEM images and figures 4d-f the corresponding unprocessed TPL intensity maps of three colloidal assemblies illuminated with linearly polarized light 7 ACS Paragon Plus Environment


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(λ = 750 nm). Compared to the relatively large size of the colloidal assemblies, the experimental

Figure 4: (color online) Shape control of the TPL maps. (a, b and c) SEM micrographs of three patterns; (d, e and f) corresponding TPL maps where the tilted white bars indicate the incident polarization. maps present a well-resolved pattern composed of several spots of different intensity located near the structure edges. The number, extent and shape of the bright spots as well as the symmetry of the recorded maps clearly depend on the footprint of the super–structure. These remarkable patterns have been consistently obtained on many differents assemblies of randomly oriented plasmonic particles displaying identical footprints and consistently recur when the polarization of the excitation beam is rotated by angles corresponding to symmetries in the structures: the possible influence of shape imperfections or any local defect on the general patterns can therefore be disregarded. Moreover, one could expect the TPL signal emerging from a collection of non-interacting gold nano-objects to be simply connected to the number of particles simultaneously present in the excitation beam focal spot. Surprisingly, the subwavelength patterning observed in Figure 4 strongly suggests that the optical response of the 3D particle assemblies is largely dictated by the interparticle coupling giving rise to the low energy band in the far-field spectra. In the following, we address the influence of structure morphology and interparticle coupling on the formation of these modal patterns using systematic numerical simulations. 8 ACS Paragon Plus Environment

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Z

Ro

ri

X

Y

Figure 5: (Color online) Schematic picture of a triangular nanoparticle assembly deposited on a glass substrate (the vectors ri define the particle locations in the super–structure). The system is swept by a focused light beam having its center at the position R0 . The triplet (X ,Y, Z) defines the cartesian frame and the TPL intensity IT PL (R0 , ω ) is computed pixel per pixel by scanning the vector R0 . To faithfully account for the experimental configuration, our numerical tool associates a realistic optical gaussian beam 49 with a generalized propagator derived from a three–dimensional Green Dyadic Method (3D-GDM) 47,50 It allows to precisely compute the local electromagnetic field inside any arbitrary 3D metal architecture placed on a substrate. The TPL signal emitted by the illuminated sample is computed from the local electric field distribution E(R0 , ri , ω ), where ri labels the location of the ith metal particle and R0 is the position of the light beam center (Figure 5). The TPL intensity can then be described by the equation: N Z

IT PL (R0 , ω ) = η (ω ) ∑ 2

i=1 vi

[|E(R0 , ri , ω )|2 ]2 dri ,

(1)

where ω is the angular frequency of the laser and η (ω ) represents an effective ω –dependent nonlinear coefficient associated with the metal. When working under monochromatic illumination, this term reduces to a constant factor. Finally N describes the total number of gold particles inside the 3D super–structures and vi label the particle volumes. In order to solve the local field distributions E(R0 , ri , ω ) inside the ith metal particle upon optical excitation, the Green dyadic tensor inside the plasmonic structures is calculated by first discretizing the volume of the metallic



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Figure 6: (color online) (Left) Top view of the simulated structure that consists of an hexagonal array of 100 nm gold spherical particles. The lattice parameter h is tuned to control the coupling in the simulations. (Right) simulated images: (A) h = 150 nm, (B) h = 120 nm, and (C) h = 105 nm. Two incident polarizations indicated by a white bar have been considered. particles with a hexagonal lattice of cells. 49 In a second step, the integration of the squared local electric field intensity on the whole structure volume gives rise to the TPL signal expected for a particular position of the Gaussian beam waist center. Finally, by raster scanning the light beam on the sample, the experimental acquisition is simulated. Therefore, the TPL images are computed through a complete self–consistent scheme including all the mutual interactions between the plasmonic entities and the substrate. 49 The optical constant for gold has been taken from Johnson and Christy, 51 while the substrate was modeled with a refractive index of 1.5. We first address the influence of interparticle electromagnetic coupling on the formation of the TPL maps and present a sequence of simulations for two typical polarizations and three different values of the lattice parameter h in Figure 6. We assume that the super-structures are composed of identical gold nanospheres placed on an hexagonal planar lattice (Figure 6 a). In each case, the excitation of SP on individual particles causes a characteristic field enhancement compared to the


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incident electromagnetic wave intensity. First, we consider the case of a lattice parameter h=150 nm corresponding to an interparticle spacing of 50 nm (Figure 6b). In this dilute configuration, the sphere–sphere self–consistent interactions are very weak and result in a uniform signal recorded over the triangular array. The individual response of each building block rather than the collective response of the whole super–structure is observed. When the lattice parameter is decreased to 120 nm, clear patterns can be distinguished in the computed TPL map (Figure 6 c). Finally, when further decreasing the separation between the plasmonic particles to 5 nm (h = 105 nm in Figure 6 d), a much better agreement with the experimental results is obtained. This clearly demonstrates that the experimentally observed patterning of the TPL signal results from the emergence of collective SP modes due to interparticle coupling. The extreme sensitivity of the patterns to the lattice parameter h that is reported here is consistent with an optical coupling mediated by an induced dipole mechanism, which is known to vary as h−3 . 30 Next, we show that the modal pattern arising from the electromagnetic coupling between the constituents of the assembly can be controlled by adjusting the direction of the polarization of the incident excitation and recording the corresponding TPL maps. Figures 7 a-d display the experimental TPL maps obtained for four different in-plane polarizations for a structure with triangular footprint. Figures 7e-h present the corresponding simulated images computed for a particle separation of 5 nm and a simulated beam waist of 300 nm. The simulated maps satisfactorily reproduce the experimental data. In particular, the distributions of intensity, which display the same spot patterns and the external polarization dependency are both very well reproduced by the model. For an incident polarization parallel to the side of the triangle, a single and weak TPL spot is observed on the distal apex with two bright spots on the proximal side. Some residual discrepancies between theory and experiment could arise from inhomogeneities in interparticle spacing or from the fact that the profile of the curved top layer has been neglected in our simulations. More realistic simulations would however require computing ressources beyond our current possibilities. Finally, the field intensity distributions observed on triangular shaped assemblies display the same topography and polarization dependence as the one observed on smaller bulk nanoprisms suggest-



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Figure 7: (color online) TPL maps evolution with the rotation of incident polarization. Experimental (a–d) and theoretical (e–h) TPL images of a 1000 nm side triangular structure presented in the SEM micrograph in panel (b) of Figure 4. The direction of the in–plane polarization is indicated in the upper right corners. The intensity color scale of (a–d) and (e–h) is similar to that of previous figures. The details of the simulation method used for panels (e) to (h) are given in the main text. ing that the plasmon modes of 3D assemblies of electromagnetically coupled metallic colloids mimick those of smaller bulk particles 54 . Similar experiments performed on bulk nanoprisms of identical morphologies have shown a quite different polarization dependence of the TPL maps. 25 This behaviour change comes from the specific nature of the surface plasmons supported by the two types of objects. Whereas the plasmon modes of three–dimensional assemblies investigated here arise from the electromagnetic coupling between the dipolar surface plasmons of the closely packed nanospheres, the SP modes of bulk nanostructures of identical morphology are similar to the well-known Fabry-Pérot modes of optical cavities. 10 Additional numerical simulations of the modal characteristics of 3D gold particle assemblies are presented in supplementary information. A comparison with those of bulk metallic structures of identical morphologies highlights these 12 ACS Paragon Plus Environment

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differences.

Conclusion In conclusion, the experiments reported in this paper provide clear evidence that it is possible to design original plasmonic patterns tunable with the light polarization by assembling mono-disperse colloidal gold particles into 3D superstructures. These composite plasmonic objects sustain specific plasmon modes according to their shapes and profiles that result from the self–consistent coupling between the gold particles. The small interparticle distances enable a strong electromagnetic coupling causing the formation of plasmon modes delocalized over all the structure. Electrodynamic calculations have confirmed the physical origin of this new plasmonic modal shaping, demonstrating the interest of using gold nanoparticle assemblies for ultracompact opto–electronic devices. Several impacts are associated with light confinement around these new plasmonic structures. These designable mesas are promising candidates for the increase of local field enhancement, and the possibility of light energy storage in tiny volumes of matter. 52 Porous structures like these nanoparticle assemblies are ideally suited to increase the interaction between light and photoactive molecules. The optical physics related to the control of light confinement might also have important impact on the future solution for the miniaturization of both chemical and biological plasmonic sensors. 53 Finally, the novel CA-CFA assembly method described here paves the way for fabricating other interesting plasmonic structures, such as chiral nanostructures or left–handed materials for the plasmonics.

Acknowledgement The authors thank funding support from CPER Gaston Dupouy 2007-2013. This work was supported by the European Research Council (ERC) (Grant ERC-2007-StG Nr 203872 COMOSYEL to E. D.), the French Agence Nationale de la Recherche (Grants ANR-08- NT09-451197-PlasTips to E. D. and ANR–09–NANO–P214-3610.1063-Aubaine to D. P.), the massively parallel comput-



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ing center CALMIP in Toulouse and the German Research Foundation (DFG) via priority program SPP135.

Supporting Information Available The supplementary information provides additional information (LDOS spectra and maps) about the plasmon modes of the 3D gold particle assemblies investigated here and compares these modes with the ones supported by bulk metallic structure of identical morphologies.

This material is

available free of charge via the Internet at http://pubs.acs.org.

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Figure 8: Table of Contents (TOC) Image


Plasmonic Shaping in Gold Nanoparticle Three ... - ACS Publications

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