NANO LETTERS

CTAB Mediated Reshaping of Metallodielectric Nanoparticles

Carla M. Aguirre, Tara R. Kaspar, Corey Radloff, and Naomi J. Halas*,,,
Rice Quantum Institute, Department of Chemistry, Department of Electrical and Computer Engineering, Rice UniVersity, Houston, Texas 77251
Received August 28, 2003; Revised Manuscript Received September 30, 2003

2003 Vol. 3, No. 12 1707-1711

ABSTRACT
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We report on the dramatic chemical reshaping of metallodielectric nanoparticles upon exposure to cetyltrimethylammonium bromide (CTAB) in aqueous solutions. Metal nanoshells possessing a silica core with a gold shell were observed to undergo a morphological change from their initial shell structure to that of large, elongated gold nanoparticles or toroids. This reaction is dependent on the chemical species available in solution and on the metal shell thickness on the nanostructure. Surprisingly, dissolution of the silica core due to the presence of CTAB was also observed during the reshaping of the nanoshells.

The bottom-up approach of nanostructure synthesis/ fabrication from molecular precursors has been very successful. Large quantities of monodisperse nanoparticles having a wide range of compositions and structures can now be synthesized.1-6 Long-range arrays of planar metal lines and metal island structures have also been fabricated using chemical methods.7,8 It remains a major challenge, however, to develop new chemical synthetic approaches to nanoparticle synthesis to obtain a further variety of more complex nanoscale shapes, for an increasingly wide range of applications. One approach has been to use preformed nanoparticles as building blocks to assemble new nanostructures. For example, metal nanoparticles can be assembled onto a variety of nanoparticle substrates to create metallodielectric nanostructures,9-11 including nanostructures of reduced symmetry,12,13 or used as templates for fabricating new nanoparticles.14-16 An alternative approach is to modify the nanoparticle growth reaction in situ to favor geometric and morphological changes in the final nanoparticle. Recent work has demonstrated that it is possible to fabricate branched CdSe nanocrystals of tunable size by controlling the growth kinetics during different phases of the reaction to favor growth along specific crystal facets of the material.17 To create anisotropic metal nanoparticles, a similar in situ growth control can be achieved by the inclusion of surfactants in the growth solution. Metal nanoparticles including nanorods,18-21 nanocubes,6,22 and nanotubes15 are some examples of particles that have been prepared using surfactant-based methods. The size and shape of the surfactant micelles provide control over particle morphology during nanoparticle growth.23 The selective

adsorption of surfactant molecules and their respective counterions on certain crystallographic facets during particle growth is also believed to affect nanoparticle shape.15,24 Studies that have attempted to characterize the mechanisms controlling the size and shape of metal nanoparticles produced through a surfactant-mediated approach have found the process to be highly dependent on the various chemical species in solution and the thermodynamic stability of the nanoparticle crystalline domains.15,21,25-27 Virtually all prior work in this area has focused on the role of the surfactant in nanoparticle synthesis. The structure and geometry of metal nanoparticles can also be modified after synthesis. Specifically, metal nanoparticles have been converted from one geometry to another using pulsed laser irradiation28-31 and photoinduced and thermalinduced conversion processes.32,33 Very little attention has been paid to the reshaping of nanoparticle morphology through chemical techniques.34,35 In this letter we report a surfactant-mediated reshaping of metallodielectric silicagold core-shell nanostructures, producing new nanostructure morphologies in a highly consistent manner. We have found that the nanoparticle reshaping is dependent upon the presence of CTAB, and that the final morphology depends on the reactant environment of the nanostructure and also on the morphology of the starting nanostructure. Specifically, we have observed the room temperature reshaping of the gold shell to form highly asymmetric gold rod-like or beanlike structures attached to silica nanoparticles, and gold toroids. We also have observed that the silica nanoscale structures present reshape and ultimately dissolve over time. In this study, we have identified several parameters that affect this remarkable chemical reactivity.

Rice Quantum Institute. Department of Chemistry. Department of Electrical and Computer Engineering. * Corresponding author: halas@rice.edu. 2003 American Chemical Society

10.1021/nl034712+ CCC: $25.00 Published on Web 11/12/2003

Figure 1. SEM image of a typical nanoshell batch consisting of particles having a 122 ( 15 nm diameter silica core and 12 nm thick gold shell. Inset: bright and dark field TEM images reveal various facets of the polycrystalline gold shell.

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The nanoshells used in these studies were fabricated by a method described in detail elsewhere.9 A number of different nanoshell batches were used in the course of these experiments. The nanoshells consisted of a 122 ( 15 nm diameter silica core with a gold shell that was varied in thickness from 10 ( 1 to 17 ( 2 nm. Figure 1 shows a scanning electron micrograph (SEM) and bright and dark field transmission electron micrographs (TEM) of as-prepared gold nanoshells having a 12 nm gold shell. Small defects can be seen in the SEM image of nanoshells in Figure 1. Various crystalline domains are apparent from the TEM micrographs (inset). The polycrystalline structure of the metallic shell is a result of the colloid-nucleated growth mechanism involved in the fabrication process. After fabrication, all nanoshell batches were centrifuged twice and redispersed in ultrapure water. No particle flocculation was observed during this process, and nanoshells prepared in this manner were observed to be stable for over six months. To eliminate adsorbed species from the surface of the nanoshells, some nanoshell batches were further purified by dialysis. Nanoshell samples cleaned through this process will be referred to as dialyzed nanoshells. In a typical dialysis, 40 mL of nanoshells in aqueous solution

was transferred into a regenerated cellulose membrane dialysis bag (Spectra-Por, 6-8k MWCO). The bag was suspended in a reservoir of ultrapure water and gently stirred overnight. Because of the unique morphology of gold nanoshells, where their plasmon-derived optical resonance is highly dependent upon the relative size of the inner and outer dimensions of the metal layer,9,36,37 any changes in their morphology are easily detected using UV-visible spectroscopy. The precise nature of the shape changes was confirmed through TEM and SEM analysis. Aqueous solutions of gold nanoshells were prepared containing various amounts of the cationic surfactants CTAB and cetyltrimethylammonium choride (CTAC). The typical nanoshell concentration was of 5 109 particles/mL. No changes were seen for gold nanoshells suspended in CTAC solutions, regardless of shell thickness or CTAC concentration. Gold nanoshells dispersed in aqueous CTAB solutions underwent a slow reshaping of their gold shell layer. These changes were independent of the surfactant concentration used in the range of 0.1 M to 1 mM. At very low surfactant concentrations (<0.1 mM) the changes were markedly slower. All experiments detailed here are for nanoshells dispersed in 1 mM CTAB solutions. After a few days in CTAB solution, the nanoshells began to degrade, and the formation of holes in the originally complete gold shell was clearly observed, Figure 2a. Additionally, when these samples were dried on a TEM grid, the presence of small gold nanoparticles was observed, which were not present in the original solution (Figure 2a, inset). The structural changes correlate with a broadening of the extinction spectrum of these solutions, Figure 2e. A broader and weaker resonant optical adsorption peak corresponds to that of incomplete gold nanoshells having numerous sizable defects. After about one week, the gold has begun to coalesce, forming larger, irregular gold particles on one side of the silica core, Figure 2b. This coincides with the evolution of the broad peak centered at 580 nm seen in Figure 2e. No significant changes in the UV-vis spectra are observed beyond this

Figure 2. Micrographs showing the decomposition of gold nanoshells in a CTAB solution at (a) 2 days (inset is a TEM image of this sample showing gold nanoparticles around the remains of the gold shell), (b) 5 days, (c) 1 month, and (d) 2 months. Figures with dark backgrounds are SEM micrographs while those with light backgrounds are TEM micrographs. (e) Extinction spectra of gold nanoshells in a 1 mM CTAB solution over 5 days. After 5 days a peak at 580 nm appeared, indicating the presence of large gold nanoparticles.
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Figure 3. Micrographs of relatively thick (17 nm) nanoshells after six weeks in a CTAB solution. There is little evidence of the original silica core, leaving hollow toroidal gold particles. SEM images have a dark background, while TEM images have a light background.
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Figure 4. Raman spectra taken of (a) bare nanoshells and (b) CTAB-reshaped gold nanoshells. In the latter, a large peak attributed to a Au-Br bond appears at 179 cm-1.

stage, since this broad extinction spectrum appears to be less sensitive to further changes in nanostructure morphology. Long-term changes were therefore monitored exclusively through electron microscopy. After a period of one month we begin to see evidence in our SEM and TEM images of etching of the silica core (Figure 2c). Curiously, the etching appears to initiate within the silica core particle, forming what appear to be hollow vesicles. After two months what remains are large, elongated gold nanoparticles with very little if any of the original silica core remaining (Figure 2d). We have also studied the influence of metallic shell thickness on the final surfactant-reshaped product. It was observed that in the case of nanoshells having a thicker gold shell (17 nm), the reshaping over a six-week period led to toroid-shaped nanostructures shown in both SEM and TEM micrographs in Figure 3. In the case of thicker shells, the reshaping of the metal does not completely destroy the original shell. This is most likely influenced by the presence of fewer fissures on the as-grown nanoshells and a larger size of the crystalline domains observed for thicker shells. Furthermore, with thicker metal shells there is a decrease in surface area available for interaction with the surfactant, thus possibly decreasing the influence of the surfactant on the metal shell structure. This thickness dependence could be further exploited to control the final shape of the metal nanoparticles influenced by CTAB. Note that again we observe that the silica core has been essentially completely etched from the nanostructure after a long period in CTAB solution. The slow coalescence of the gold nanoshell into solid nanoparticles observed in our experiments is reminiscent of an Ostwald ripening process.17 Given that the as-grown polycrystalline gold shell is not the most thermodynamically favored shape, it should be somewhat susceptible to reshaping. In particular, the polycrystalline surface of the shell makes it sensitive to any reactivity specific to certain crystallographic facets. Fink et al. reported the sintering and coalescence of alkylammonium bromide-capped gold nanoparticles deposited on a flat surface.38,39 During anisotropic
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Ostwald ripening, the growth of certain crystallographic facets is favored at the expense of the dissolution of other more unstable crystallographic facets.15,17 Although in the present case it is not known if solid gold particles are soluble in aqueous CTAB solutions, it is known that the adsorption of halide ions on gold surfaces is accompanied by an increased mobility of gold surface atoms.40 More recently, the coalescence of citrate-capped gold nanoparticles in solution and on a surface has been reported.34 In this work the gold nanoparticles were found to undergo a dissolution resulting in smaller gold clusters, which then recoalesce into irregular gold nanoparticles. On the basis of their observations, it is possible in our studies that the CTAB forms a strong complex on the gold shell surface, which in turn is readily dissolved into solution. This mechanism could be supported by the small gold nanoparticles observed in Figure 2a and 2c. Once dissolved, these particles may likely recoalesce into larger existing particles through Ostwald ripening. Other groups have studied the chemical specificity of CTAB extensively.19,21,23,27 The surfaces of short gold nanorods fabricated in the presence of CTAB and an additional cosurfactant are known to be enclosed by high-energy unstable {110} facets of gold.41 In a recent study, it was demonstrated that the adsorption of bromide ions to these high-energy crystal facets results in unusually strong Raman enhancements.42 The presence of the Au-Br vibration at 174 cm-1 was exclusive to gold nanorods and was not observed for gold colloidal particles not bound by {110} crystal facets. In our experiments, Raman spectra were taken on a Renishaw Ramascope using a 760 nm excitation source. Prior to sample preparation, the nanoshell solutions underwent the standard centrifuging and redispersing cleaning procedure to remove any excess CTAB from solution. The samples were prepared by depositing a small amount of the concentrated aqueous solution onto cleaned glass slides to form a film of aggregated nanoshells. The samples were then dried in a vacuum desiccator overnight. Figure 4 shows the Raman spectra of both bare gold nanoshells and nanoshells
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after one month in a CTAB solution. A very sharp and distinctive peak at 179 cm-1 that can be attributed to the Au-Br vibration is observed for the CTAB reshaped nanoshells. From this result we can infer the attachment of the bromide ion to the gold surface, which may be preferentially occurring on the unstable {110} facet of gold, providing further evidence of the reshaping mechanism described above. The experiments performed with nanoshells were repeated using dialyzed nanoshells. The dialyzed nanoshells were found to be stable in CTAB solutions for over four months, with no reshaping observed. This observation suggests that species adsorbed to the surface of the gold nanoshell, probably left over from the gold shell reduction, are necessary for the reshaping process to take place. Because the reactivity is seen only with nondialyzed nanoparticles, we believe that this extra dialysis step eliminates a key species from the surface of the nanoshell. As has been suggested by many studies on CTAB-mediated nanoparticle growth, it is possible that the stabilization and formation of different nanocrystalline shapes is due to the presence of other molecular species during nanoparticle synthesis, possibly byproducts of the reduction reaction. In a control experiment, dialyzed gold nanoshells were dispersed in CTAB solutions containing varying amounts of all the chemicals used for nanoshell synthesis. It was only through the addition of chloroauric acid that the original reactivity and decomposition of the gold nanoshell was recovered. The surprising reactivity of the silica cores of the gold nanoshells is clearly observed through closer inspection of the nanoshell-CTAB solution in Figure 2c. After one month in the CTAB solution, the silica core is significantly altered and appears to have been etched away. Bare silica particles and APTES-coated silica particles, such as those used for nanoshell synthesis, dispersed in CTAB solutions showed no such decomposition. It is known that alkylammonium hydroxides can be used to etch silica.43 Such alkylammonium hydroxides can be formed through the interaction of alkylammonium salts (such as CTAB) and metal oxides.44 Given the very slow etch rates reported for silica by alkylammonium hydroxide molecules,43 we have calculated that our silica nanoparticles would be completely etched over approximately a one month period in the presence of these molecules. In addition it is possible that the APTES coating protects the surface of the silica particles leading to the preferential etching of the interior of the silica cores. We have observed a distinct chemical reactivity of metallodielectric nanoparticles in solutions containing relatively low concentrations of an ionic surfactant. Gold nanoshells underwent a radical morphological change when mixed with the surfactant CTAB. The addition of CTAB to a solution of nanoshells possessing a relatively thin gold shell results in the formation of large gold nanoparticles that appear to melt together in solution. For relatively thick gold shells, the inherent shell structure is preserved while the shells still appear to melt into toroid-shaped particles. In both these cases the silica cores of the nanoshells appear to have been etched. The remarkable chemical reactivity observed for gold
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nanoshells in CTAB solutions opens interesting questions into the role of surfactant species in the synthesis and stabilization of metal nanoparticles. The opportunity to perform in situ controllable, structural modification of composite nanoparticles opens interesting avenues for the fabrication of more complex nanoparticle morphologies possessing their own unique optical45 and structural properties. Acknowledgment. The authors acknowledge funding from the Army Research Office, NASA, The Robert A. Welch Foundation, The Air Force Office of Scientific Research, Texas Advanced Technology Program, and the National Science Foundation. References
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