Detecting patchy nanoparticle assembly at the single-particle level.

Patchy colloidal particles offer a unique platform to explore and investigate spatially inhomogeneous colloidal interactions. In the present work we provide direct, in situ experimental observation at the single particle level on the colloidal interaction driven formation of a heterodimer, consisting of a patchy nanorod and a sphere. The gold nanorods employed during the experiments feature positively charged tip regions, while the side of the rods is covered by surface grafted PEG. The driving force of the assembly is the electric double layer interaction between the nanorod and the nanosphere possessing opposite surface charge. The great advantage of using gold heterodimers is that their optical scattering spectrum characteristics are known to be very sensitive to the actual structure of the assembly due to plasmon hybridization. This was exploited to determine the structure of the heterodimer in situ upon formation in aqueous medium. The results indicate, that despite the attractive patches being located at the nanorod tips, for the given particle pairs the spheres readily bind to the side region of the nanorods in the aqueous medium during the assembly. Finite element simulations of the electric double layer interaction reveal that this is the energetically favorable configuration for the given heterodimer. This work demonstrates the potential of in situ experiments performed at single particle level for the characterization of self-assembling structures, which can contribute to the development of rationally designed nanoscale building blocks.

Assembling patchy nanorods with spheres: limitations imposed by colloidal interactions.

For gold nanorods the intrinsic shape-anisotropy offers the prospect of anisotropic assembly, provided that their region-selective surface modification can be realized. Here we developed nanorods with a patchy surface chemistry, featuring positively charged molecules in the tip region and polymer molecules at the sides by careful control of molecule concentrations during ligand exchange. When these patchy nanorods are assembled with small negatively charged spherical particles, electric double layer interaction can direct the assembly of two nanospheres at the opposite ends of the nanorods. The PEG chains promote the selectivity of the procedure. As the size of the nanospheres increases, they start to shift towards the side of the nanorod due to increased van der Waals interaction. When the relative size of the nanospheres is even larger, only a single nanosphere is assembled, but instead of the tip region, they are attached to the side of the nanorods. The apparent cross-over of the region-selectivity can be interpreted in terms of colloidal interactions, i.e. the second spherical particle is excluded due to nanosphere-nanosphere electric double layer repulsion, while the large vdW attraction results in a side positioning of the single adsorbed spherical particle. The results underline the importance of absolute values of the different interaction strengths and length scales in the programmed assembly of patchy nanoscale building blocks.

The structure and properties of graphene on gold nanoparticles.

Graphene covered metal nanoparticles constitute a novel type of hybrid material, which provides a unique platform to study plasmonic effects, surface-enhanced Raman scattering (SERS), and metal-graphene interactions at the nanoscale. Such a hybrid material is fabricated by transferring graphene grown by chemical vapor deposition onto closely spaced gold nanoparticles produced on a silica wafer. The morphology and physical properties of nanoparticle-supported graphene are investigated by atomic force microscopy, optical reflectance spectroscopy, scanning tunneling microscopy and spectroscopy (STM/STS), and confocal Raman spectroscopy. This study shows that the graphene Raman peaks are enhanced by a factor which depends on the excitation wavelength, in accordance with the surface plasmon resonance of the gold nanoparticles, and also on the graphene-nanoparticle distance which is tuned by annealing at moderate temperatures. The observed SERS activity is correlated with the nanoscale corrugation of graphene. STM and STS measurements show that the local density of electronic states in graphene is modulated by the underlying gold nanoparticles.