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DOI: 10.1002/adma.200702994

Gold/Iron Oxide Core/Hollow-Shell Nanoparticles**

By Elena V. Shevchenko, Maryna I. Bodnarchuk, Maksym V. Kovalenko, Dmitri V. Talapin, Rachel K. Smith, Shaul Aloni, Wolfgang Heiss, and A. Paul Alivisatos*
Assembling several materials into a single nanoparticle (NP) is an attractive way to design systems possessing diverse physical and chemical properties.[114] In multicomponent systems, one can expect novel and unique properties that originate from collective interactions between the constituents.[15,16] Multicomponent nanoparticles exhibit distinct optical,[11,17] catalytic,[18,19] and photocatalytic[20] properties. To date, several morphologies of multicomponent nanoparticles have been reported. The general strategy to synthesize multicomponent materials is rst to prepare nanoparticles of one material, and then use them as nucleation seeds to deposit the other components. Signicant progress has been made in the synthesis of semiconductor nanoparticles with epitaxial shells, while the synthesis of nanoparticles that combine components with very different lattice parameters still faces many challenges. To date, a number of heterostructures have been successfully synthesized through seed-mediated approaches.[2,912] However, only a few hybrid nanoparticles show a reasonable level of control over particle size distribution and homogeneity in composition. It was recently shown that CoPt3/Au dumbbells,[2] PbSe/Aux heterostructures,[21] Au/Fe3O4 dumbbells and solid core/shell structures,[5] anisotropic Fe2O3 nanoparticles decorated with a polycrystalline Au shell,[22] and Pt/CoO core/hollow-shell nanoparticles[23] can be obtained at the nanoscale. Iron oxide based
[*] Dr. E. V. Shevchenko,[+] Prof. A. P. Alivisatos, Prof. D. V. Talapin,[++] Dr. S. Aloni The Molecular Foundry, Lawrence Berkeley National Laboratory Berkeley, CA 94720 (USA) E-mail: eshevchenko@anl.gov; apalivisatos@lbl.gov M. I. Bodnarchuk, Dr. M. K. Kovalenko, Prof. W. Heiss Institute of Semiconductor and Solid State Physics, University Linz 4040 Linz (Austria) Dr. R. K. Smith Lawrence Berkeley National Laboratory Berkeley, CA 94720 (USA) [+] Present addresses: Center for Nanoscale Materials, Argonne National Laboratory, Argonne, IL 60439-4806, USA. [++] Present address: Department of Chemistry, University of Chicago, Chicago, IL 60637, USA. [**] The work at the Molecular Foundry, Lawrence Berkeley National Laboratory, and at the Center for Nanoscale Materials was supported by the Ofce of Science and Ofce of Basic Energy Sciences of the U.S. Department of Energy under Contract Nos. DE-AC02-05CH11231 and DE-AC02-06CH11357, respectively. We acknowledge Dr. Jeffrey B. Kortright for helpful discussions. M.I.B., M.V.K., and W.H. acknowledge nancial support from the Austrian Science Foundation FWF (Project start Y179) and from the Austrian Nanoinitiative (Project NSI). Supporting Information is available online from Wiley InterScience or from the author.

materials are being studied intensively because of their potential as magnetic resonance imaging (MRI) agents.[24] The combination of magnetic and high-contrast X-ray materials can be a promising route towards the design of dual agents allowing both MRI and X-ray detection. From this viewpoint, composite structures based upon nanometer-sized iron oxide and gold particles have a lot of potential. In addition, the concept of gold-based nanomaterials was recently proposed to design dual MRI/optical agents.[25,26] Materials combining noble metals and oxides are also of practical interest because of their advanced catalytic properties.[23] The deposition of metal oxides onto noble metals signicantly affects their optical propertiesas the plasmon resonance frequency is shifted. This may be utilized to tune the frequency of plasmon resonances, and to control plasmon exciton interactions between semiconductors and noble metals in multicomponent periodic arrays.[2729] Here we report a facile and reproducible technique to synthesize gold (core)/ iron oxide (hollow-shell) nanoparticles with controllable thickness and morphology of the outer oxide shell for the rst time. We analyze the different aspects of our synthetic approach and discuss the optical and magnetic properties of these composite materials. We also demonstrate the strategy to grow hollow nanoshells encapsulating several nanoparticles. These systems may be of particular interest to investigate the interactions between individual nanoparticles in conned environments. The synthesis of gold nanoparticles encapsulated within hollow iron oxide shells involves three steps: i) synthesis of Au nanoparticles; ii) deposition of an iron shell around the gold core; and iii) oxidation of the iron shell to form a hollow iron oxide shell by means of the Kirkendall effect (see Supporting Information, Fig. S1). Gold (core)/iron oxide (hollow shell) nanoparticles were prepared via the thermal decomposition of Fe(CO)5 at the surface of the gold nanoparticles in octadecene in the presence of capping molecules (oleylamine and oleic acid) to terminate the growth of the bulk phase. Gold nanoparticles catalyzed the decomposition of Fe(CO)5 and lowered the decomposition temperature from approximately 150 to 135 8C. Since the capping ligands at the surface of the preformed gold seeds could affect the ability of iron to deposit on the seeds surface, we examined the deposition process onto gold NPs coated with three different capping ligands: oleylamine, hexadecylamine, and dodecanethiol. Au nanoparticles stabilized with different capping ligands were obtained according to the literature.[30,31] The key idea of this approach is that

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as-formed, very polydisperse nanoparticles are etched by adding digestive ripening agents such as amines, thiols, etc.[31] We found that iron can precipitate on a gold surface stabilized by any of these capping ligands (Fig. S1). However, the best particle size distribution of composite material was achieved in the case of dodecanethiol-capped gold nanoparticles (Fig. S1). Thus, we have chosen dodecanethiol-stabilized gold nanoparticles as the model system to study different aspects of iron oxide shell formation. Iron oxide shells grown in the presence of oleylamine only are rather irregular, are polycrystalline, and in some places are connected to the gold core (Fig. 1a). Electron energy loss spectroscopy (EELS) has demonstrated the porous morphology of the oxide shells and conrms the existence of extended bridges between the gold core and oxide shell (inset of Fig. 1a). Polycrystallinity of the oxide shell and multiple goldoxide interface connections suggest that there are multiple nucleation sites of iron at the surface of the gold. We have found that the addition of oleic acid to the reaction mixture changes the morphology of the gold/iron oxide core/hollow-shell nanoparticles, leading to more uniform shells formed around the gold cores (Fig. 1bd); even though the oxide shells are still polycrystalline (Fig. 2b). The thinnest oxide shell around the gold nanoparticles was about 2 nm thick with a 1:1 molar ratio

of oleylamine to oleic acid (Fig. 1d). Increasing the relative concentration of oleic acid led to the formation of a precipitate. Decomposition of Fe(CO)5 in octadecene in the presence of oleylamine, followed by air oxidation in the absence of gold nanoparticles, is known to give hollow iron oxide nanoparticles.[3234] In order to elucidate the role of oleic acid, we injected Fe(CO)5 at 180 8C into an oleylamineoctadecene mixture containing different amounts of oleic acid with no gold particles. We have found that the introduction of oleic acid led to a size decrease of hollow iron oxide nanoparticles (Fig. S2 of Supporting Information), and at a 1:2 oleylamine/oleic acid molar ratio, no nucleation and growth of iron occurred at 180 8C. We assume the formation of stable complexes at our reaction temperature (presumably, iron oleate), which slowed down the iron nucleation and growth. The decrease in the thickness of the iron oxide shells with an increase of the oleic acid concentration (Fig. 1) could also be a result of etching of iron oxide shells by oleic acid. In order to rule out this possibility we added oleic acid to the solution of puried hollow iron oxide nanoparticles dissolved in octadecene and kept it at 180 8C for 2.5 h. Transmission electron microscopy (TEM) studies revealed that gold (core)/iron oxide (hollow shell) nanoparticles did not undergo any morphological changes. Reuxing of the crude reaction solution

Figure 1. ad) Transmission electron microscopy (TEM) images of gold/iron oxide (core/hollow-shell) nanoparticles synthesized with different amounts of oleic acid. Molar ratio of oleylamine/oleic acid: a) 1:0, b) 1:0.1, c) 1:0.3, and d) 1:1. e) Optical spectra of 4.5 nm Au without and with 2.5 and 3.3 nm iron oxide hollow shells, and Fe core (4.5 nm)/iron oxide shell (2.5 nm) nanoparticles. Inset in (a) gives the electron energy loss (Fe) spectrum of Au/iron oxide (core/hollow-shell) nanoparticle acquired in scanning TEM (STEM) mode.

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Figure 2. High-resolution TEM (HRTEM) images of gold/iron oxide (core/ hollow-shell) nanoparticles synthesized with a) 1:0 and b) 1:0.4 oleylamine/ oleic acid molar ratios.

containing the gold/iron oxide core/hollow-shell nanoparticles at 300 8C prepared with oleic acid leads to the formation of core/shell nanoparticle structures with very thick oxide shells and a signicant amount of small solid iron oxide nanoparticles (Fig. S3 of Supporting Information). The further growth of the iron oxide shell at high temperatures can be associated with transfer of the iron precursor through the existing pores in the shell or through cracks (formed during high-temperature reuxing) in the oxide shell. No dewetting[35] of iron oxide was found even after prolonged (ca. 12 h) thermal treatment, neither in solution nor in particles deposited on the carboncopper TEM grids. When Fe(CO)5 was replaced with iron(III) oleate, only large, polydisperse (ca. 1015 nm) Au nanoparticles were formed at 180 8C. Further increasing of the reaction temperature up to 300 8C initiated the nucleation and growth of solid iron oxide and precipitation of gold onto the walls of the reaction ask. This observation supported the idea

of stabilization of the iron precursor by forming a strong iron oleate complex. Depending on the solvent, oxidative agents, and temperature used, thermal decomposition of Fe(CO)5 in nonpolar solvents is known to give mainly two crystalline iron oxide phases: Fe3O4 and g -Fe2O3.[33,34,3638] X-ray diffraction (XRD) and HRTEM studies of our gold core/iron oxide hollow-shell nanoparticles revealed the high polycrystallinity of the iron oxide shell. Electron diffraction (ED) allowed us to exclude the a-Fe2O3 phase (Fig. S4 of Supporting Information). The oxide shell usually consists of 510 domains. Line broadening of XRD and ED patterns associated with the small crystal size domains leaves the possibility of the coexistence of g -Fe2O3 and Fe3O4 phases,[39,40] which have only a slight difference between their crystal lattices (ca. 1% difference in the cubic lattice constant of the same spinel crystal structure). In our case, the multidomain structure of the iron oxide shell suggests that up to 80% of atoms are at or close to the surface of the hollow shell. This makes the precise analysis of the crystalline structure complex. In the case of a close match of lattice parameters, epitaxial growth of a shell is expected.[41] Crystallographically directed growth of the second material at the surface of the preformed seeds is widely used to protect the emitting core of semiconductor nanoparticles by depositing a shell with a wider band gap onto it.[41,42] The surface of nanoparticles can be terminated by different planes, and planar epitaxy of the second component can grow evenly only along certain crystallographic directions, leading to anisotropic morphologies of composite nanoparticles. For example, epitaxial growth of cobalt nanoparticles was observed at the surface of titanium dioxide rod-like particles.[9] Only dumbbell-like gold/iron oxide composite nanoparticles were synthesized in octade while that of cene.[3,5] The lattice constant of Au is 4.08 A ; the proposed mechanism of dumbbell Fe3O4 is 8.35 A formation was based on epitaxial growth of iron oxide on the gold seeds.[3,5] In solvents such as benzyl or phenyl ethers, aromatic groups are believed to donate electrons to gold and promote the additional nucleation of iron oxide at the gold surface, leading to the formation of polycrystalline, irregularly shaped solid core/shell structures,[5] which then fused into a continuous shell at 300 8C. Heating of our reaction solution above 220 8C in the presence of oleic acid was accompanied by the growth of irregularly shaped thick solid iron oxide shells around gold nanoparticles and the formation of solid iron oxide nanoparticles if oleic acid was added to the reaction mixture. As mentioned above, the oxidation of iron nanoparticles depends signicantly on the surface, temperature, and oxidative agent. We attribute the discrepancy in our observations and previously published results to differences in the reaction conditions: i) different approaches and different capping ligands were used to synthesize the gold seeds; ii) different iron precursors; and iii) different temperature regimes were used to deposit and oxidize iron as compared to the literature.[5] We believe that the different morphologies of the Au/iron oxide core/hollow-shell nanoparticles are a

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result of different nucleation barriers for different iron precursors. In the case of a low nucleation barrier, such as in the case of thermal decomposition of Fe(CO)5, one can expect random deposition of iron onto the surface of the seed particles, leading to core/shell type structures. Precursors with a high nucleation barrier, such as iron oleate or Fe(acac)3, will tend to precipitate mainly on certain facets of the seeds. These facets can either be more active or better developed, less passivated by organic molecules.[2] In this case, preferential deposition of the second component will result in the growth of nanoparticles, possessing well-dened morphologies.[2,21] The population of separate iron oxide nanoparticles in the nal crude solution heated at 180 8C was negligible, which highlights the heterogeneous nucleation of iron at the surface of gold nanoparticles. We believe that gold catalytically promotes the deposition of multiple nuclei of iron on its surface; these nuclei then independently grow and form a polycrystalline iron shell around the gold core. Passing the oxygen through the reaction solution converts the iron shell into iron oxide via the Kirkendall effect.[23] Complete oxidation of iron leads to the formation of the void between the gold core and iron oxide as a result of the different diffusion rates of oxygen and iron through the outer shell. Different types of interactions occur between nanoparticles in a solution. Dipolar interactions between PbSe nanoparticles were found to be responsible for the nanoparticle chaining leading to the formation of continuous PbSe nanowires.[43] Also it was shown that some capping ligands can affect electrostatic interactions between nanoparticles, resulting in the formation of a variety of nanoparticle binary superlattices.[28] The presence of a charge at the nanoparticle surfaces can provide extra stability to nanoparticles in nonpolar solvents and can affect particleparticle interactions.[28,44,45] Previously, we have found that in the presence of oleic acid the surface of gold nanoparticles is negatively charged while in the presence of trioctylphosphine oxide (TOPO) their surface is neutral.[28] We assume that in the presence of TOPO, Au nanoparticles can come close to each other, and fast decomposition of Fe(CO)5 can trap several Au nanoparticles in one shell (Fig. 3), leading to the formation of

multiple gold cores encapsulated inside one single iron oxide shell. It is evident from Figure 3 that in some oxide shells, gold nanoparticles are interconnected, indicating the fusion of gold nanoparticles before or after deposition of the oxide shell. Gold nanoparticles are known to fuse slowly after deposition on a substrate at room temperature.[46] Heating of these Au multicore/iron oxide hollow-shell nanoparticles at 300 8C in solution led to the fusion of gold nanoparticles and to the partial cracking of the oxide shell. We believe that our approach can be further extended to encapsulate nanoparticles of different types and sizes. Potentially it can provide a unique opportunity to investigate the interactions between individual nanoparticles in conned environments. Gold nanoparticles, in the size range from approximately 3 to 20 nm, are known to exhibit strong surface plasmon resonance (SPR) absorption at around 520 nm.[47,48] As shown in Figure 1, our Au nanoparticles show an SPR peak at 525 nm, consistent with previous studies.[5] The exact position of the plasmon resonance band depends on particle size and shape, and the medium surrounding the particles.[47] Coating of gold nanoparticles with a dielectric material leads to a shift of the SPR frequency. The refractive index of any type of iron oxide is higher (2.33.1) than that of gold (0.47) or hydrocarbon solvents (ca. 2); the presence of an oxide shell should strongly affect the plasmon band position. We found that a hollow iron oxide shell shifted the SPR peak of Au nanoparticles to about 595 nm (Fig. 1e), which is in good agreement with computed data (ca. 600 nm).[5] The study of the magnetic properties was performed on nanoparticles with hollow iron oxide shells, approximately 3 nm in thickness, lled with 4.5 nm gold NPs. Hysteresis loop measurements (Fig. 4a) demonstrate their superparamagnetic behavior at room temperature. These particles became ferromagnetic below the blocking temperature (Tb, Fig. 4a), which was estimated from peak magnetization of the zero eld cooled (ZFC) curve to be approximately 65 K (Fig. 4b). The magnetic properties of nanoparticles can be affected by structural distortions at the surface and their structural disorders.[49,50] In the case of hollow nanoparticles, the contribution of surface effects should be even higher.

Figure 3. Left: scheme demonstrating the possible synthesis mechanism of hollow iron oxide nanoparticles containing multiple gold cores, as shown in the TEM image on the right.

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magnetic eld of 1 T manifested pronounced exchange bias in the gold/iron oxide (core/hollow-shell) nanoparticles (Fig. 4c). Signicant coercivity enhancement below the spin-glass transition temperature (ca. 42 K in the case of g -Fe2O3 nanoparticles)[52] indicated that extra energy is required to switch the spins pinned by the exchange interactions with the frozen spin-glass surface layer (Fig. 4c). In summary, we have described an approach to synthesize binary colloidal nanoparticles, consisting of gold nanoparticles encapsulated in a hollow iron oxide shell. The growth of such structures is based on random nucleation of iron on the preformed gold nanoparticles. Subsequent oxidation of the iron shell by oxygen leads to the formation of the hollow oxide shell. Adjustments of the gold particleparticle interaction by adding subsequent organic molecules to the Figure 4. a) Magnetization (M) loops for gold/iron oxide (core/hollow-shell) nanoparticles, about reaction solution makes it possible to 13 nm in size (gold core is ca. 4.5 nm in diameter, iron oxide thickness is ca. 3 nm); b) Zero- encapsulate several gold cores inside one eld-cooled (ZFC) and eld-cooled (FC) magnetizations versus temperature (T), measured in a eld iron oxide shell. Optical data indicate a (H) of 100 Oe (Tb indicates blocking temperature); c) Magnetization loops cooled to different signicant shift of the frequency of the temperatures under the applied external eld of 1 T; The inset in (c) demonstrates the temperature plasmon resonance of gold nanoparticles dependence of the exchanged bias eld Hex. as a result of the deposited iron oxide shell. Imminent control over the porosity and thickness of the oxide shell can make the use of such nanoparticles as a catalyst Thus, the signicant decrease of saturation magnetization in carbon monoxide conversion possible.[53] Magnetization (ca. 2230 emu g1), observed in the case of gold/iron oxide measurements reveal the superparamagnetic behavior of the (core/hollow-shell) nanoparticles (Fig. 4c), as compared to that gold/iron oxide core/hollow-shell nanoparticles at room of bulk ferrimagnetic Fe3O4 (84 emu g1) and ferromagnetic temperature. Shifted hysteresis loops after eld-cooling shows g -Fe2O3 (74 emu g1) can be explained by canting of the an exchange bias, originating from the presence of a surface spins; saturation of these requires very high magnetic spin-glass-like layer at the nanoparticle surface. elds.[40] It was shown that surface spin disorder can lead to the appearance of exchange anisotropy, and the existence of a spin-glass-like phase around the magnetic particles was proposed.[49,51] The origin of this surface spin-glass layer is Experimental associated with broken bonds and the translational symmetry Chemicals: Octadecene, toluene, ethanol, oleic acid (OA), distortion. This generates randomness in the exchange oleylamine, AuCl3, Fe(CO)5, sodium borohydride, and didodecyldiinteractions that extend to atomic layers from the particles methylammonium bromide (DDAB) were purchased from Aldrich. surface. In the case of g -Fe2O3 nanoparticles, the spin-glass Oleic acid and oleylamine were of technical degree of purity. All chemicals were used as received. surface layer was estimated to be about 0.6 nm.[52] Being Synthesis of Au NPs: The detailed synthesis of Au nanoparticles is cooled below the spin-glass transition temperature in an described in the literature [29, 30]. We scaled the quantities of all external eld, spins of the spin-glass layer are aligned and chemicals reported in Ref. [29] by a factor of 3. Different capping frozen along the applied eld. In hysteresis loop measureligands were used as agents for digestive ripening of as-formed ments, these spins keep their direction and pin the reversible polydisperse Au nanoparticles. Oleylamine (3 mL), hexadecylamine (1 g), and dodecanethiol (2.4 mL) were used as digestive ripening spins of the core, leading to the appearance of the exchange agents [31]. After digestive ripening, Au nanoparticles were prebias. An increase of the temperature leads to thermal cipitated with 30 mL of ethanol, dried and redispersed in 9 mL of uctuation of the net moments of the surface layer, which toluene. tend to be polarized by the core- particle moments. The shift of Synthesis of Gold/Iron Oxide Core/Hollow-Shell NPs: 1 mL of magnetization curves measured after a eld cooling in a toluene solution containing approximately 7 mg of Au nanoparticles

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was dried under air or a N2 gas ow. Then 20 mL of octadecene and 0.1 mL of oleylamine or oleylamineoleic acid mixture (the molar ratios are given in the caption of Fig. 2) were added to the ask, and the solution was sonicated for 5 min. The solution was kept under vacuum at 80 8C for 30 min, and then 0.1 mL of Fe(CO)5 was injected into solution and kept at 180 8C for 30 min. The colloidal solution was cooled to 100 8C, and air was passed though the solution for approximately 10 min. The excess of unreacted species and capping ligands was washed away by using a tolueneethanol solvent nonsolvent combination followed by centrifugation. No size-selection procedures were performed. Characterization of NPs: Nanoparticles were deposited onto ultrathin 300-mesh carbon supported by copper grids (Type A, Ted Pella, Inc.) that were pre-cleaned from formvar by dipping for 15 s into toluene. Gold and gold/iron oxide nanoparticles were deposited from toluene solutions. A Tecnai G2 S-Twin electron microscope (TEM) operating at 200 kV was used for imaging of Au and Au/iron oxide nanoparticles. High-resolution TEM (HRTEM) and electron energy loss spectroscopy were performed using a JEOL 2100-F 200 kV eld-emission analytical transmission electron microscope. Optical absorption spectra were taken with a Shimadzu UV/vis spectrophotometer UV2101. Magnetic properties of the samples were measured with a Quantum Design MPMS-2 SQUID magnetometer in the temperature range from 5 to 300 K and under the applied elds up to 1 T. Received: December 1, 2007 Revised: February 29, 2008 Published online: June 2, 2008

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