Herein, we report the novel strategy for the synthesis of complex 3-dimensional (3D) nanostructures, mimicking the linker molecule-free 3D arrangement of six Au nanospheres at the vertices of octahedrons. We utilized 3D PtAu skeleton for the structural rigidity and deposited Au around the PtAu skeleton in a site-selective manner, allowing us to investigate their surface plasmonic coupling phenomenon and near-field enhancement as a function of sizes of nanospheres, which are directly related to the intrananogap distance and interior volume size. The resulting 3D Au hexamer structures with octahedral arrangement were realized through precise control of the Au growth pattern. The complex 3D Au hexamers were composed of six Au nanospheres connected by thin metal conductive bridges. The standard deviation of the metal conductive bridges and Au nanospheres was within ca. 10%, exhibiting a high degree of homogeneity and precise structural tunability. Interestingly, charge transfer among the six Au nanospheres occurred along the metal conductive bridges leading to surface plasmonic coupling between Au nanospheres. Accordingly, electric near fields were strongly and effectively focused at the vertices, intrananogap regions between Au nanospheres, and interior space, exhibiting well-resolved single-particle surface-enhanced Raman spectroscopy signals of absorbed analytes.
Silver double nanorings with circular intra-nanogaps between two nanorings of different diameters were synthesized without a linker molecule to confine an incident electromagnetic field in a single entity. We used on-demand, rational, and systematic multi-stepwise reactions consisting of (1) selective etching of gold, (2) rim-on deposition of platinum, (3) eccentric growth of gold, and (4) concentric growth of silver. The resulting silver double nanorings exhibited a high degree of homogeneity in both shape and size, with strongly coupled circular hot zones (or “hot halos”, referring to the circular intra-nanogaps capable of focusing the near electromagnetic field) resulting from strong surface plasmon coupling between the inner and outer nanorings. Remarkably, these silver double nanorings exhibited strong, stable, and reproducible single-particle surface-enhanced Raman scattering signals without blinking. The signals appeared independently of polarization directions, which is a unique feature of a circular hot halo. The estimated enhancement factor was between 2 × 108 and 7 × 108. The measured limit of detection was 10–7 M in bulk concentration, and the signal appeared 570 s after sample exposure.
Here we report a synthetic pathway toward Au truncated octahedral dual-rim nanoframes wherein two functional facets are formed including (1) eight hot nanogaps formed by hexagonal nanoframes embracing core circular nanorings for near-field focusing and (2) six flat squares that facilitate the formation of well-ordered arrays of nanoframes through selfassembly. The existence of intra-nanogaps in a single entity enables strong electromagnetic near-field focusing, allowing single-particle surface-enhanced Raman spectroscopy. Then, we built "all-hot-spot bulk SERS substrates" with those entities, wherein the presence of truncated terraces with high homogeneity in size and shape facilitate spontaneous self-assembly into a highly ordered and uniform superlattice, exhibiting a limit of detection of attomolar concentrations toward 2-naphthalenethiol, which is 6 orders lower than that of monorim counterparts. The observed low limit of detection originates from the combined synergic effect from both inter-and intraparticle coupling in a superlattice, which we dubbed "all-hot-spot bulk SERS substrates".
Three-dimensional (3D) nanoframe structures are very appealing because their inner voids and ridges interact efficiently with light and analytes, allowing for effective optical-based sensing. However, the realization of complex nanoframe architecture with high yield is challenging because the systematic design of such a complicated nanostructure lacks an appropriate synthesis protocol. Here, we show the synthesis method for complex 3D nanoframes wherein two-dimensional (2D) dual-rim nanostructures are engraved on each facet of octahedral nanoframes. The synthetic scheme proceeds through multiple executable on-demand steps. With Au octahedral nanoparticles as a sacrificial template, sequential processes of edge-selective Pt deposition and inner Au etching lead to Pt octahedral mono-rim nanoframes. Then, adlayers of Au are grown on Pt skeletons via the Frank-van der Merwe mode, forming sharp and well-developed edges. Next, Pt selective deposition on both the inner and outer boundaries leads to tunable geometric patterning on Au. Finally, after the selective etching of Au, Pt octahedral dual-rim nanoframes with highly homogeneous size and shape are achieved. In order to endow plasmonic features, Au is coated around Pt frames while retaining their geometric shape. The resultant plasmonic dual-rim engraved nanoframes possess strong light entrapping capability verified by single-particle surface-enhanced Raman scattering (SERS) and show the potential of nanoprobes for biosensing through SERS-based immunoassay.
In this Letter, a rational and stepwise method for the solution-phase synthesis of asymmetric Au split nanorings by adopting Au nanoprisms as a template has been demonstrated. The selective chemical etching of Au nanoprism tips activated the surface reactivity of edges and led to the selective deposition of Pt at the periphery of Au nanoplates. By controlling the total amount of Pt on the edges, different degrees of split Au@Pt nanorings were obtained; the subsequent Au coating around the Au@Pt scaffold eventually resulted in asymmetric Au hexagonal split nanorings. Their surface plasmonic features as a function of split degrees were investigated, including straight nanorods, bent nanorods, split nanorings, and full nanorings. The electrical field focusing using single-particle surface-enhanced Raman spectroscopy was evaluated under different polarization angles of the incident light for two different structures with the point gap and line gap between two arms.
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