Abstract Engineering the nucleation and growth of plasmonic metals (Ag and Au) on their pre‐existing seeds is expected to produce nanostructures with unconventional morphologies and plasmonic properties that may find unique applications in sensing, catalysis, and broadband energy harvesting. Typical seed‐mediated growth processes take advantage of the perfect lattice match between the deposited metal and seeds to induce conformal coating, leading to either simple size increases (e.g., Au on Au) or the formation of core–shell structures (e.g., Ag on Au) with limited morphology change. In this work, we show that the introduction of a thin layer of metal with considerable lattice mismatch can effectively induce the nucleation of well‐defined Au islands on Au nanocrystal seeds. By controlling the interfacial energy between the seed and the deposited material, the oxidative ripening, and the surface diffusion of metal precursors, we can regulate the number of islands on the seeds and produce complex Au nanostructures with morphologies tunable from core‐satellites to tetramers, trimers, and dimers. 
                        more » 
                        « less   
                    
                            
                            Engineering surface strain for site-selective island growth of Au on anisotropic Au nanostructures
                        
                    
    
            Controlled growth of islands on plasmonic metal nanoparticles represents a novel strategy in creating unique morphologies that are difficult to achieve by conventional colloidal synthesis processes, where the nanoparticle morphologies are typically determined by the preferential development of certain crystal facets. This work exploits an effective surface-engineering strategy for site-selective island growth of Au on anisotropic Au nanostructures. Selective ligand modification is first employed to direct the site-selective deposition of a thin transition layer of a secondary metal, e.g., Pd, which has a considerable lattice mismatch with Au. The selective deposition of Pd on the original seeds produces a high contrast in the surface strain that guides the subsequent site-selective growth of Au islands. This strategy proves effective in not only inducing the island growth of Au on Au nanostructures but also manipulating the location of grown islands. By taking advantage of the iodide-assisted oxidative ripening process and the surface strain profile on Au nanostructures, we further demonstrate the precise control of the islands’ number, coverage, and wetting degree, allowing fine-tuning of nanoparticles’ optical properties. 
        more » 
        « less   
        
    
                            - Award ID(s):
- 1808788
- PAR ID:
- 10382348
- Date Published:
- Journal Name:
- Nano Research
- ISSN:
- 1998-0124
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
- 
            
- 
            Abstract Facet‐selective etching and deposition, as determined by the landscape of surface energy, represent two powerful methods for the transformation of noble‐metal nanocrystals into nanostructures with complex shapes or morphologies. This review highlights the use of these two methods, including integration of them, for the fabrication of novel monometallic and bimetallic nanostructures with enhanced properties. We start with an introduction to the role of surface capping in controlling the facet‐selective etching or deposition on the surface of Ag nanocrystals, followed by a case study of how to maneuver etching and deposition at different facets of Pd nanocrystals for the fabrication of nanoframes. We then introduce the use of galvanic replacement to accomplish selective etching and deposition on two different facets in an orthogonal manner, transforming Pd nanocubes into Pd−Pt octapods. By complementing galvanic replacement with a chemical reduction reaction, it is also feasible to control the rates of these two reactions for the conversion of Ag nanocubes into Ag@Ag−Au concave nanocubes and Ag@Au core‐shell nanocubes. These transformation methods not only greatly increase the shape diversity of metal nanocrystals but also offer nanocrystals with enhanced plasmonic and/or catalytic properties.more » « less
- 
            Abstract Reliability, shelf time, and uniformity are major challenges for most metallic nanostructures for surface‐enhanced Raman spectroscopy (SERS). Due to the randomness of the localized field supported by silver and gold nanopatterns in conventional structures, the quantitative analysis of the target in the practical application of SERS sensing is a challenge. Here, a superabsorbing metasurface with hybrid Ag–Au nanostructures is proposed. A two‐step process of deposition plus subsequent thermal annealing is developed to shrink the gap among the metallic nanoparticles with no top‐down lithography technology involved. Because of the light trapping strategy enabled by the hybrid Ag–Au metasurface structure, the excitation laser energy can be localized at the edges of the nanoparticles more efficiently, resulting in enhanced sensing resolution. Intriguingly, because more hot spots are excited over a given area with higher density of small nanoparticles, the spatial distribution of the localized field is more uniform, resulting in superior performance for potential quantitative sensing of drugs (i.e., cocaine) and chemicals (i.e., molecules with thiol groups in this report). Furthermore, the final coating of the second Au nanoparticle layer improves the reliability of the chip, which is demonstrated effective after 12 month shelf time in an ambient storage environment.more » « less
- 
            Abstract Photonic integrated circuits require various optical materials with versatile optical properties and easy on‐chip device integration. To address such needs, a well‐designed nanoscale metal‐oxide metamaterial, that is, plasmonic Au nanoparticles embedded in nonlinear LiNbO3(LNO) matrix, is demonstrated with tailorable optical response. Specifically, epitaxial and single‐domain LNO thin films with tailored Au nanoparticle morphologies (i.e., various nanoparticle sizes and densities), are grown by a pulsed laser deposition method. The optical measurement presents obvious surface plasmon resonance and dramatically varied complex dielectric function because of the embedded Au nanoparticles, and its response can be well tailored by varying the size and density of Au nanoparticles. An optical waveguide structure based on the thin film stacks of a‐Si on SiO2/Au‐LNO is fabricated and exhibits low optical dispersion with an optimized evanescent field staying in the LNO‐Au active layer. The hybrid Au‐LNO metamaterial thin films provide a novel platform for tunable optical materials and their future on‐chip integrations in photonic‐based integrated circuits.more » « less
- 
            Metal–organic coordination networks at surfaces, formed by on-surface redox assembly, are of interest for designing specific and selective chemical function at surfaces for heterogeneous catalysts and other applications. The chemical reactivity of single-site transition metals in on-surface coordination networks, which is essential to these applications, has not previously been fully characterized. Here, we demonstrate with a surface-supported, single-site V system that not only are these sites active toward dioxygen activation, but the products of that reaction show much higher selectivity than traditional vanadium nanoparticles, leading to only one V-oxo product. We have studied the chemical reactivity of one-dimensional metal–organic vanadium – 3,6-di(2-pyridyl)-1,2,4,5-tetrazine (DPTZ) chains with O 2 . The electron-rich chains self-assemble through an on-surface redox process on the Au(100) surface and are characterized by X-ray photoelectron spectroscopy, scanning tunneling microscopy, high-resolution electron energy loss spectroscopy, and density functional theory. Reaction of V-DPTZ chains with O 2 causes an increase in V oxidation state from V II to V IV , resulting in a single strongly bonded (DPTZ 2− )V IV O product and spillover of O to the Au surface. DFT calculations confirm these products and also suggest new candidate intermediate states, providing mechanistic insight into this on-surface reaction. In contrast, the oxidation of ligand-free V is less complete and results in multiple oxygen-bound products. This demonstrates the high chemical selectivity of single-site metal centers in metal–ligand complexes at surfaces compared to metal nanoislands.more » « less
 An official website of the United States government
An official website of the United States government 
				
			 
					 
					
 
                                    