Current Opinion in Colloid & Interface Science 16 (2011) 128134

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Current Opinion in Colloid & Interface Science

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / c o c i s

Gold nanorod crystal growth: From seed-mediated synthesis to nanoscale sculpting

Catherine J. Murphy , Lucas B. Thompson, Davin J. Chernak, Jie An Yang, Sean T. Sivapalan, Stefano P. Boulos, Jingyu Huang, Alaaldin M. Alkilany, Patrick N. Sisco
Department of Chemistry, University of Illinois at Urbana-Champaign, 600 S. Mathews Avenue, Urbana, IL 61801, USA

a r t i c l e

i n f o

a b s t r a c t
Gold nanorods have received tremendous attention in recent years due to their exciting potential applications in chemical sensing, biological imaging, drug delivery and phototherapeutics. A seed-mediated growth procedure in aqueous solution has been developed to produce these colloidal materials in reasonable quantities, with tunable shape. Details of the reaction chemistry, role of impurity ions, and their inuence on the nal product shape are still under debate. Subsequent chemistry on preformed nanorods can yield a variety of new shapes and functionalities for numerous applications. 2011 Elsevier Ltd. All rights reserved.

Article history: Received 9 September 2010 Received in revised form 29 December 2010 Accepted 4 January 2011 Available online 12 January 2011 Keywords: Gold Nanorod Synthesis Shape

1. Introduction 1.1. Shape matters It is well-known that small amounts of nely-divided gold appear brilliant ruby-red when dispersed in a transparent medium (e.g., stained glass). We now understand these optical effects to be due to surface plasmons, collective oscillations of conduction band electrons in a metal, when the metal particle size approaches the electron mean free path length (~10100 nm) [13]. While the physics for the case of small conducting spheres was worked out by Mie in 1908, only with the advent of improvements in synthesis and computation ability have the optical properties of small conducting cylinders in a colloidal solution been adequately examined. We dene here a nanorod to be a nanoscale particle with an aspect ratio (length/width ratio) that is between 1 and ~2025; higher aspect ratio materials we will call nanowires (as long as the diameter is less than ~ 100 nm). Our group, along with others, has developed synthetic procedures to prepare gold nanorods in solution, which can give a relatively high yield, excellent shape monodispersity and reasonably tight control over the dimensions of the particles in the sub-100 nm range [1,46]. Evidence for rod-shaped particles is usually obtained by transmission electron microscopy, but for gold, the optical spectra of the plasmons

Wet chemical syntheses of gold nanorods have been reported for nearly a decade in the literature. Recent new data on the fundamentals of the colloidal crystal growth have appeared, and ne-tuned sculpting of nanocrystal shape can yield new properties. Corresponding author. Tel.: +1 217 333 7680; fax: +1 217 244 3186. E-mail address: murphycj@illinois.edu (C.J. Murphy). 1359-0294/$ see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.cocis.2011.01.001

are very informative (Fig. 1). Nanospheres of gold, ~ 550 nm in diameter, show one plasmon band at ~ 520 nm if spectra are taken in aqueous solution with a standard spectrophotometer. (The position of the plasmon band is well-known to be sensitive to the local dielectric constant of the media, and the aggregation state of the particles; we will consider here that the nanoparticles are well-dispersed in the same solvent for comparison.) Nanorods show two plasmon bands, commonly ascribed to light absorption (and scattering) along both the long axis (longitudinal plasmon band) and the short axis (transverse plasmon band) of the colloidal particles (Fig. 1) [16]. Subtleties such as quadrupole resonances, which can also yield what appear to be regular plasmon bands, are examined in a number of excellent reviews [2]. As the aspect ratio increases, the position of the longitudinal plasmon band red-shifts, and the transverse plasmon band position stays relatively constant at ~ 520 nm (Fig. 1). Thus, the particle shape dictates what wavelengths of light can be absorbed, and elastically scattered; gold nanorods of moderate aspect ratio (25) display plasmon bands with tunable maxima from ~700 to 900 nm, and high-aspect ratio nanorods exhibit a longitudinal plasmon band past 1500 nm [16]. The plasmon that results from incident light illumination also leads to the creation of large electric elds near the nanoparticle surface. Nanorods are very interesting shapes from this point of view, as this electric eld is enhanced at the tip of a rod, compared to a spherical particle [7,8]. These enhanced elds offer increased sensitivity for chemical sensing modalities such as surface-enhanced Raman scattering (SERS), in which the Raman signals from molecules increase enormously in intensity, if the molecules are within ~10 nm of a metal nanoparticle surface [68]. The potential application space of gold nanorods for biology is enormous, and relies on the tunability of the plasmon band position

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size of gold nanorods mimics that of virus particles (for example, tobacco mosaic virus is 18 nm 300 nm) and there are efforts to use gold nanorods as in vivo reporters and therapeutics [1416]. Finally, the large extinction coefcients of the plasmon bands of gold nanorods lead to strong absorption, followed by heat release to the environment. Because the nanorod plasmon band position can be tuned to the near-infrared water window of the tissue, photothermal therapy, in which near-infrared light illumination leads to heat that can destroy diseased cells, is possible [917]. For true in vivo applications, issues of toxicity, biodistribution and metabolism must be addressed; gold nanorods are indeed being explored along these dimensions [11,12,18]. For the potential of gold nanorods in all of these applications to be realized, improvements in fundamental understanding of the crystal growth processes that lead to controllable rods are needed [19,20]. It is not yet possible, for example, to a priori know what set of reaction conditions will yield gold nanorods that are 5 nm in diameter and has an aspect ratio suitable for light absorption at 1200 nm. Therefore, the scope of this article is on synthesis, mechanism, and post-synthetic modications of gold nanorods that can chemically tune their surfaces.

2. The seed-mediated growth approach to gold nanorods: general concepts The creation of gold nanorods can be accomplished in many ways, from lithographic deposition of thin gold lms on a substrate followed by various chopping procedures [21], to electrochemical deposition in hard nanotube templates [22,23], to photochemical reactions in solution [24]. Our approach, seed-mediated growth, is a multistep controlled redox reaction [46] that is performed in room temperature aqueous solution, suitable for scaling up; indeed, gold nanorods based on our method can now be purchased from major chemical vendors. Our seed-mediated approach utilizes small seed particles (~1.54 nm diameter) that are rst synthesized from ~104 M gold salt (HAuCl4) and excess strong reducing agents to promote isotropic growth over anisotropic growth. These seed particles are then added to a growth solution that contains additional gold salt, a weak reducing agent, and a structure-directing agent to control the nal particle shape. Ascorbic acid is an ideal secondary reducing agent because it is too weak to reduce the additional gold salt in the growth step from Au3+ to Au0 alone, in our reaction conditions. This allows for the growth to occur over a long time (minutes to hours), which aids in anisotropic growth. The structuredirecting agent we use is cetyltrimethylammonium bromide (CTAB), a cationic surfactant well-known to form rodlike micelles on its own in water [4]. In fact, our original idea behind the use of CTAB (at 0.1 M under our conditions, far larger than its critical micelle concentration) was that it would serve as a soft template to promote nanorod formation as the gold seeds grew upon further metal ion addition [4,25]. We do not consider CTAB's templating ability as its primary function now, however, although we have found that all chemical components of this molecule, from its alkyl chain length to its counterion, are critical to retain the ability to synthesize rods [2628]. Indeed, impurities such as iodide at part-permillion levels in commercial CTAB batches can ruin the synthesis of gold nanorods [28,29], although judicious modication of synthetic conditions with iodide can yield interesting shapes (to be discussed below). The nal gold nanorods obtained all bear a bilayer of CTAB on their surfaces [3032], and therefore our view, detailed below, is that CTAB's primary function is to adsorb to the growing seed particles and block crystal growth along certain faces [6]. A recent report nds CTAB's micellar nature to be a key factor in nanorod purication from other shapes due to depletion attraction forces of surfactant micelles [33]. It is possible to use other surfactants in the place of CTAB, if conditions are sufciently altered (although bromide counterions, thus far, are still present) [34]. We note

Fig. 1. Top: ultravioletvisible spectra of short gold nanorods with aspect ratios (A) 1.42 0.32, (B) 1.82 0.49, (C) 2.31 0.55, (D) 2.65 0.43, and (E) 2.80 0.37. The UVvis spectra were normalized to the same absorbance at ~515 nm for clarity. Lower panels: transmission electron micrographs of the gold nanorods corresponding to spectra A, B, C, D, and E; all scale bars are 100 nm.

with particle shape [913]. In addition to chemical sensing via SERS or other methods (e.g., plasmon peak shifting as a function of aggregation state or local refractive index), the elastic light scattering of gold nanorods makes them visible at the single-particle level in darkeld optical microscopy, suitable for in vivo tracking [3,12]. Different aspect ratios of gold nanorods scatter different wavelengths of light, leading in principle to different colored tracking probes. The

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that a recent exhaustive review article on anisotropic metal nanoparticles that covers some of the same points we raise here has appeared [35].

promote anisotropic growth. Slight changes in growth conditions can lead to more needle-like nanorod morphologies [40]. 4. Proposed mechanisms of gold nanorod growth in the absence of silver ions In the original three-step seeding method, gold nanorods can be prepared with high aspect ratio (~20), starting from 3.5 nm seeds prepared by sodium borohydride reduction of gold salt in the presence of citrate ions, and in the absence of silver ions [4]. Highresolution transmission electron microscopy and selected area electron diffraction analysis have shown that the gold nanorods prepared in the absence of silver ions are pentatetradedral twins, where the cubic symmetry of the native gold face-centered cubic lattice is broken by twinning (Fig. 2) [41]. The cross sectional view of these rods is pentagonal; each end of the rod consists of ve triangular facets that are Au{111} faces, and the sides of the rods are either Au {100} or Au{110} [4]. The surfactant structure (head group, hydrocarbon chain length, and counterion) is found to play a crucial role to prepare these high aspect ratio gold nanorods; for example, bromide is far superior to chloride or iodide for nanorod production, even if the CTA+ cation is intact [27]. Indeed, the high concentrations of CTAB required for gold nanorod synthesis appear to be a requirement for high bromide concentrations (as judged by the success of synthesis if CTAB is lowered by a factor of 10 but the growth solutions are supplemented with sodium bromide) [27]. Derivatives of CTAB with the same head group and bromide counterion but with different tail lengths (10, 12, and 14 carbons) produced nanorods with tunable aspect ratios; the longer tails produced longer rods, and the 10-carbon version of CTAB was capable of only producing spheres [26]. Based on the electron diffraction data of gold nanorods and the accumulative evidences of the importance of the CTAB structure and concentration, we postulated a general mechanism for the growth of gold nanorods in the absence of silver ions [6]. Our mechanism proposes a differential adsorption of CTAB to different crystal faces followed by thermodynamically favorable intermolecular interactions of the 16carbon cetyl chains to promote surface adhesion (Fig. 2). More specically, we postulated that CTAB adsorbs preferentially to the side of rods, Au{100} or Au{110}, via chemisorbed bromide counterions, over the ends of the rods, which display Au{111} faces. This preferential binding regime agrees with the size of the quaternary ammonium head group relative to the larger binding sites available on the {100} and {110} faces of the crystalline rods [6,41]. The binding of CTAB, ultimately as a bilayer [6], on the side of the rod blocks the deposition of further gold to the side and promotes the growth from the ends [6]. Liz-Marzan et al. proposed that the CTAB micellar structure also promoted the deposition of metal at the tips of gold seed particles that are also surrounded by CTAB [42]. Specically, they proposed that ions and then tightly bind to CTA+ AuCl 4 ions rst displace Br micelles. Addition of ascorbic acid then reduced AuCl 4 to AuCl2 at the micelle surface, and the rate of growth of the different nanorod facets would be determined by the approach of the micelle and thus gold species toward the facets of the gold seed particles that are also covered with CTAB. After calculating the surface potential of metal ellipsoids in 1 mM NaCl, Liz-Marzan et al. showed that this potential decays more rapidly at the nanorod tip than along its length, and thus the micelle can more readily approach the tips of the rods than the sides and allow deposition of gold. It is noted by this group and ours, however, that an asymmetry in the seed must be present to create an asymmetric electric eld initially, possibly in the form of a twinning plane or stacking fault [6,42]. An improved synthesis method of high-aspect-ratio gold nanorods increased the nanorod yield by adjustment of the pH of the growth solution [43]. The addition of sodium hydroxide to raise the pH of the growth solution from 2.8 to 3.5 greatly increases the yield of nanorods

3. Two pathways to gold nanorods: with and without additive impurity ions The seed-mediated growth approach can be broadly broken down into two distinct pathways that are distinguished by the presence or the absence of additive silver ions, at low enough levels that the silver could be considered an impurity. The addition of silver into the growth solution likely alters the chemistry at the interface of the growing particle and the growth solution, which we will discuss further in the upcoming section on the proposed mechanisms. Other impurity metal salts can be used, but silver is the most reliable [27]. For high aspect ratio rods (aspect ratio ~ 20), a three-step seeding method is used where adjusting the timing of reaction in each step, rods of increasing aspect ratios (from ~4 to 18) can be obtained [4]. The general procedure starts with preformed seed particles, as described above, and three sets of growth solutions containing additional gold salt and CTAB. The rst growth solution is seeded with the seed particles; 1015 s later, an aliquot of this solution is used as the seed for the next growth solution; and so on. After three steps of seeding, gold nanorods of aspect ratios ~18 can be obtained, albeit in low absolute yield (~4%). Stopping the seeding process at intermediate steps generates intermediate aspect-ratio nanorods, although it is still not possible to reliably generate nanorods of arbitrary aspect ratio (e.g., aspect ratio 8 as opposed to aspect ratio 12) [4]. While one advantage of this method is the ability to scale up (compared to nanoporous template, for example), a primary disadvantage is the large proportion of gold nanospheres and other shapes that are formed, greatly reducing the yield of rods. Purication of the longest rods relies on their slow settling out of solution due to gravity. The quality of the seed particles can affect nanorod growth; in general, smaller seeds lead to more monodisperse nanorods [36,37]. Whether the seeds are single crystalline or twinned also is thought to inuence the type of rods that are formed single crystalline or twinned, as will be discussed below although for many practical purposes, the optical spectra and overall dimensions of the nal gold nanorods do not depend on the crystalline nature of the gold core. The addition of silver was an important breakthrough for the synthesis of gold nanorods as it allowed for improved shape control and yield for short aspect ratio rods (aspect ratios 16, nearly tunable in 0.5 increments) [5,38]. This is the method that has been scaled up for commercial production. The total amount of silver in the rods is enough for a few monolayers of silver on the surface of the gold core [37,39], and XPS data suggest that silver is preferentially localized on the surface [37]. The preparation of gold nanorods using this silverassisted method is not done in the same multi-step seeding format as for the silverless method above; once seed particles are added to a growth solution that contains gold salt, CTAB, ascorbic acid, and silver nitrate, the amount of silver nitrate added dictates the nal aspect ratio of the rods [5]. These rods cannot be used as seeds themselves to grow longer rods, unlike their silverless counterparts (although some additional sculpting is possible, as will be discussed later); therefore, if a higher aspect ratio gold nanorod is desired, the synthesis must be redone with a higher concentration of silver nitrate. Only aspect ratios up to ~6 can be prepared in the silver-assisted method. The yield of particles that are rod-shaped is exceptionally high (~90%) after two rounds of purication by centrifugation (Fig. 1). However, the absolute yield in terms of gold ions is less than 15%; that is, less than 15% of the gold ions that are reagents in the synthesis end up as part of a gold nanorod [39]. Simply reducing the concentrations of all reagents in the synthesis decreases nanorod yields, suggesting that reservoirs of unreduced metal ions, and CTAB, are important to

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Fig. 2. A cartoon that demonstrates the proposed mechanism of gold nanorod growth (in the absence of silver). The seed particles have different facets that allow for differential binding of the surfactant to each face. The preferential binding of the surfactant to the side Au{100} and Au{110} faces, over the {111} faces at the ends, results in blocking the nanorod growth at the sides and promotion of nanorod growth at the ends.

with the aspect ratio of ~18. To obtain higher aspect ratio nanorods, the addition of heptane into the growth solution is helpful; in this way, nanorods with an aspect ratio of ~ 20 have been prepared [25]. By further increasing the pH to 5.8, nanorods with higher aspect ratio of ~ 25 can be prepared, but with much lower shape monodispersity [43]. Zubarev has found that Au(III)CTAB complexes are capable of dissolving gold nanostructures in a shape-dependent manner; this process can be tuned to purify gold high aspect ratio nanorods and greatly improve their monodispersity [44]. We note that many other groups are working on different ways to chemically synthesize gold nanorods, or nanowires; for example, Giersig and Liz-Marzan report that HAuCl4 can be reduced with oleylamine, followed with thermal and solvent processing, to yield 1.6 nm diameter single-crystalline gold nanowires that can have lengths up to 4 m [45]. In this case the control of aspect ratio was limited, and the growth mechanism was, like for CTAB, attributed to preferential adsorption of oleylamine to different crystal facets of the growing nanorod/nanowire [45]. Murray et al. have used a gold(I) precursor, AuCl, with oleylamine and carbon monoxide as a reducing agent in a related manner to produce gold nanowires that are 2.5 nm in diameter and up to several microns long, albeit with limited control over aspect ratio [46]. 5. Proposed mechanisms of gold nanorod growth in the presence of silver ions Using a one-step seeding method, which includes AgNO3, one can prepare low aspect ratio (~ 16) gold nanorods starting from 1.5 nm seeds prepared by sodium borohydride reduction of gold salt in the presence of CTAB [6,38]. While high aspect ratio gold nanorods can be hundreds of nanometers in length, these low aspect ratio rods are tens of nanometers in length, up to about 90 nm. Guyot-Sionnest and colleagues have discussed the critical nature of the structure of the seed in determining the nal form of gold nanorods grown via the seed-mediated, silver-assisted synthesis method [47]. Specically, they found that single crystalline gold seeds produce single crystalline gold rods, while multiply twinned gold seeds produce multiply twinned gold bipyramids [47]. It is suggested that the relatively slow growth of rods during Ag+ assisted growth uniquely allows gold atoms to deposit at energetically favorable locations with no defect character, maintaining the single crystalline or twinned structure of the seeds. The critical nature of the silver species during this synthesis has been even more heavily discussed, and several groups have proposed different reasons for how the silver species can assist in the anisotropic growth of gold nanorods. One possibility is that silver bromide complexes play critical roles during nanorod formation [48]. In this scenario, the deposition of AgBr on a specic facet of gold nanorods during seed-mediated growth stabilizes the rods and directs their growth by allowing more rapid incorporation of gold on less hindered facets. The presence of silver bromide species is further

evidenced by XPS data suggesting the presence of Ag(I) and 1H NMR spectra for CTAB capped gold nanorods being identical to those of pure AgBrCTAB [48]. However, the presence of free silver bromide (as the reaction occurs above the Ksp of AgBr) could lead to spurious NMR spectra interpretation. Others have mass spectrometric evidence that AgBr 2 , as well as AuBr2 , exists at the gold surface for wellpuried nanorods that result from the photochemical synthesis method [49,50]. Hafner reports Raman evidence of the AuBr bond formation at 180 cm1, which can be lost if thiols replace adsorbed bromine on the gold nanorod surface [51]. Others, however, propose that silver bromide complexes may not explain anisotropic growth, and instead argue that underpotential deposition of a monolayer or submonolayer of elemental silver on the gold nanorod surface is of signicance [47]. Guyot-Sionnest and colleagues propose that, during seed-mediated synthesis, underpotential deposition (UPD) of silver preferentially occurs on the {110} gold facets compared to the {111} and {100} facets [47]. In this model, a silver monolayer strongly protects the {110} facet, and, though the silver may be oxidized and replaced by gold, other facets grow fastest due to their being less covered with silver. Differing degrees of silver passivation on the {110} facets should lead to varying ratios of growth on this facet and the nanorod's end facets, and this is consistent with what is observed for the standard silver-assisted growth technique (Fig. 3). Inductively coupled atomic emission spectroscopy has been used to quantify the amount of silver in rods after synthesis, and it was estimated that four monolayers worth of silver is present in rods, though the technique does not differentiate between different Ag(0) and Ag(I) [39]. EXAFS studies have suggested that Ag0 is the nal form of silver for rods grown via a different photochemical method, consistent with the possibility that elemental silver is of crucial importance not just for the standard technique used in our lab but for the variety of synthetic methods available to produce gold nanorods [52]. It is possible for other surfactants to be used in place of CTAB to give tunable gold nanorods; for example, Liz-Marzan has shown that gemini surfactants that form wormlike micelles produce well-controlled nanorods that are sufciently monodisperse to self-assemble in superlattices [34]. Even here, however, CTAB-coated gold seed particles, silver nitrate, and bromide counterions were all present, suggesting that the growth mechanisms outlined above may be operative [34]. 6. Fine-tuning the shape of gold nanorods after synthesis After nanorod synthesis, rod shapes can be ne-tuned by a variety of methods. Such methods include etching preferentially at the nanorod tips to produce shorter rods, or sharper rods; heating or laser treatment to produce lower-aspect ratio rods; or continued growth or overgrowth on rods to produce dogbone or dumbbell shaped nanoparticles, that have new plasmon features, or show different crystal faces to the solvent that might be useful for catalytic purposes (especially for more reactive metals).

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Fig. 3. One of the proposed mechanisms that explain the role of silver in the silver-assisted, seed-mediated method of gold nanorod synthesis. Underpotential deposition of silver occurs preferentially at the {110} facets of gold, leading to relatively quick growth of other facets until the slower deposition of silver on the end of the rods eventually terminates growth.

Fine-tuning the shape of nanomaterials through chemical etching after the nanomaterial is synthesized can be accomplished by various means. In many of these cases, preferential shortening of the rods occurs, and this is likely due to a lower degree of surface passivation of the rod tips compared to sides by CTAB, which more readily allows tip etching. FeCl3, for example, has been used at room temperature to signicantly shorten rods, in a controllable manner, while having little effect on widths of the rods [53]. Though ferric ions do not normally have the ability to oxidize gold under the reported reactions, the authors suggested that the presence of chloride sufciently alters the redox potential of gold so that Au(I) and Fe(II) are produced [53]. Bubbling of O2 in the presence of HCl at slightly elevated temperatures preferentially produces shortened gold nanorods as well, and so does CuCl2 treatment [54,55]. Gold nanorods can be completely dissolved with aqueous cyanide treatment in air if sufcient reagents are present, leading to the complex ion [Au(CN)2]; in this reaction too, nanorods are preferentially dissolved from the ends rst [56]. If a polymer or silica coating surrounds the rods, hollow tubes of polymer or silica can be generated by cyanide dissolution of the gold [57]. The mechanism by which preferential end-reactivity occurs is likely a composite of improved availability of surface sites (due to less CTAB on the ends of the rods compared to the sides) and higher surface energies at the ends of the rods (although one piece of evidence for higher surface energies on nanoscale particles is increased reactivity, a somewhat circular argument). Heating gold nanorods after synthesis to ne-tune shapes can also lead to ne changes in the nanorod morphology. Boiling short gold nanorods, made with silver ion present, in their aqueous reaction mixture before purication increases both their length and width in their native growth solution, but they ultimately become fatter and therefore decrease in aspect ratio [58]. We postulate that boiling water temperatures are sufcient to destabilize the CTAB bilayer surrounding the gold nanorods and thus the larger side areas of the nanorods are available for reaction; in the case of the ascorbic acidcontaining growth solution, gulonic acid (ascorbic acid's oxidation product) can reduce available metal ion leftover from the synthesis, at 100 C, to add more metal to the nanorod sides and decrease the aspect ratio [58]. Purication of the nanorods negates these reactions, and puried nanorods appear to be stable to boiling water for at least 1 h [58]. El-Sayed and colleagues showed that gold nanorods grown by an electrochemical method remain nearly constant in width but greatly decrease in length upon heating slightly over 100 C [59]. Upon heating the rods to near 600 C, the nanorods not only begin to change shape but also melt as well [59]. Gold nanorods can furthermore be shape-tuned to a dogbone or peanut shape. Addition of more ascorbic acid to short gold nanorods, at room temperature and if the growth solution containing unreduced metal ions is still present, leads to dogbone-shaped nanoparticles due to gold overgrowth on the ends of the rods [58]. The relatively large amounts of unreduced gold salt remaining in solution after synthesis are reduced by the ascorbic acid, and the reduced metal deposits onto the less CTAB covered rod tips, which themselves act as seeds to the

newly depositing metal. Dogbone or dumbbell-shaped gold nanoparticles can also be achieved by addition of more HAuCl4 to gold nanorod solutions, and this likely functions by a similar mechanism [60]. It is also worthwhile to note that the slow addition of ascorbic acid over several days to gold nanorod solutions leads to further growth of nanorods not with a dogbone shape, but with retention of the original typical nanorod shape [61]. In general, for adding more gold to gold nanorods, one must be cognizant of the redox-active species that can still be present in gold nanorod solutions. Liz-Marzan has shown that if iodide is present during silverassisted gold nanorod growth, it is possible, depending on the exact solution conditions, to grow uniformly fatter nanorods, or to grow more gold at the ends to form peanut shapes, controlled by local rates of deposition [37]. These results seemingly contradict those of Korgel et al., who found that iodide impurities in CTAB prevent nanorod formation [29]; but relative solution conditions were not identical. XPS and surface-enhanced Raman data on the nature of the metal and the halide, in Liz-Marzan's case, support the formation of chemisorbed halide on both silver and gold (silver being more on the surface than gold), and preferential binding of iodide to different crystal faces of the nanorods was invoked to explain the results [37]. Thiols are commonly used to modify gold surfaces, and work along these lines has been done for gold nanorods as well. Glutathione or cysteine can bind preferentially to, and hinder the growth of, nanorod tips during overgrowth, leading to a dramatic growth in the width of rods but little in their length [62]. In this case, these thiolated molecules are added to rod solution, followed by more growth solution. Rods gain a dogbone or a peanut shape as {111} faces grow outward from the rod, but, growth at the tips is hindered by the thiolated molecules, further growth leads to truncated octahedral shaped gold nanoparticles [62]. Gold nanorods, made with the silver-assisted method, can be grown into nanoscale octahedral by a combination of polymer coating and ultrasonication in organic solvent by selective deposition of metal onto the side facets and the ends [63]. As the nanorods become more chunky, the plasmon bands shift back towards the blue. More drastic ne-tuning of nanorod shapes, post-synthesis, can be achieved, such as the application of laser light at plasmon maximum wavelengths to gold nanorod solutions. With such treatment, rods can be made shorter or into strange shapes, as well as melted or fragmented, depending on laser parameters [64,65]. 7. Nanorods grown on surfaces and nanorodnanorod gaps All of the previous work discussed in this paper has been on the growth of gold nanorods in colloidal solution from seeds. Yet other possibilities present themselves: for example, one could immobilize the seed on a surface and attempt to grow gold nanorods on substrates. Although for practical purposes, electrodeposition of metal into hollow polycarbonate or aluminum oxide templates might be easier, the growth of nanorods on surfaces does hold fundamental interest and may result in aligned nanorods (Fig. 4).

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For instance, several groups have shown that the growth solutions used to make gold nanorods in the silverless method (e.g., CTAB, gold salt, and ascorbic acid) can be incubated with gold seed particles that have been immobilized on a surface, and nanorods do form on the surface, in spite of the inherent difculties presented in the surface itself serving as a nucleation site for growth [66,67]. Astonishingly, chemical modications of the surface can produce aligned nanorods, by a mechanism that is not yet clear [68]. If an electrochemically active surface is used, one can apply a potential to reduce gold salt to elemental gold on immobilized seed particles in the presence of growth solutions, rather than a chemical reductant such as ascorbic acid [69]. Because gold nanorods, upon light irradiation into their plasmon bands, can create large electric elds at their tips, many workers are exploring ways to line nanorods up end-to-end to enhance the electric elds experienced in the gaps for molecular electronics or chemical sensing (via surface-enhanced Raman scattering) applications. Chemical modication at the ends of gold nanorods in solution can lead to some level of alignment, with molecular-scale nanorodnanorod gaps [70,71]. On larger length scales, striped metal nanowires can be prepared by electrodeposition (e.g., gold/nickel or gold/silver) within hard templates (diameters ~360 nm) with subsequent chemical etching of the nickel or silver to produce tunable gaps (~5100 nm) between the tips of very large gold nanorods [72,73]. Gaps may also be cut cleanly through such larger nanorods by focused ion beam cutting [74]. In an interesting twist, Bjornholm et al. have linked gold seed particles with dithiol linkers; upon the addition of growth solution, metal is deposited on the seed particles away from the dithiol linker to generate linked dimers and trimers of gold nanorods [75]. Spacings of 12 nm are achievable with this method, although the nanorods do tend to fuse [75]. 8. Conclusions and future work There appears to be room for almost limitless variation in the reagents that can be used in gold nanorod syntheses and many minor variations on the general theme have appeared. Factors to consider, that frequently are not considered, include the redox potential of agents in the growth solutions; Ksp's of possible byproducts; temperature or pH-induced changes in redox potentials; and activities of the reaction byproducts (e.g., ascorbic acid's oxidation product, as noted above, can itself still reduce metal ions at elevated temperature). Arguments as to the thermodynamic stability of different crystal faces, as a mechanism for shape control, regularly appear in the literature; our own data suggest to us that kinetic

parameters may be more important, and indeed are more consistent with how delicate the synthesis can be. Far less well-explored is the notion of doing top-down sculpting chemistry on nanoscale objects themselves. The old surface science literature from the 1940s through the 1980s is full of crystal-face-selective anisotropic etches for many bulk metals and semiconductors, and could serve as a good source for future work. Y. Xia has demonstrated the etching concepts thoroughly for silver nanoparticles, and is one of the few people that have explored other precursors for gold nanoparticles besides HAuCl4 [7678]. Gold nanorods provide a clear visual indicator of their shape through the color of their solutions that is, the positions of their plasmon bands. Fine-tuning particle shape can shift the position of plasmon bands, as can various overcoating procedures (via shifts in the local refractive index of the medium). We expect that as synthetic procedures become ever more standardized and understood, designer nanoparticles with arbitrary plasmon band positions and overall dimensions can be made at will.

Acknowledgements We thank our former group members for the excellent work that has laid the foundations for current thinking. We also thank the National Science Foundation and the Air Force Ofce of Scientic Research for funding.

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Fig. 4. A schematic cartoon illustrating how gold nanorods may be grown on a surface. Growth on a substrate allows for the possibility of aligned rods with nanoscale gaps between them. Gold seeds are rst deposited on a substrate and then, upon the addition of growth solution, nanorods can be grown from the seeds resulting in arrays of nanorods on the substrate.

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