skip to main content

Explore Research Products in the NSF-PAR

Title: Large-area periodic arrays of gold nanostars derived from HEPES-, DMF-, and ascorbic-acid-driven syntheses
With arms radiating from a central core, gold nanostars represent a unique and fascinating class of nanomaterials from which extraordinary plasmonic properties are derived. Despite their relevance to sensing applications, methods for fabricating homogeneous populations of nanostars on large-area planar surfaces in truly periodic arrays is lacking. Herein, the fabrication of nanostar arrays is demonstrated through the formation of hexagonal patterns of near-hemispherical gold seeds and their subsequent exposure to a liquid-state chemical environment that is conducive to colloidal nanostar formation. Three different colloidal nanostar protocols were targeted where HEPES, DMF, and ascorbic acid represent a key reagent in their respective redox chemistries. Only the DMF-driven synthesis proved readily adaptable to the substrate-based platform but nanostar-like structures emerged from the other protocols when synthetic controls such as reaction kinetics, the addition of Ag + ions, and pH adjustments were applied. Because the nanostars were derived from near-hemispherical seeds, they acquired a unique geometry that resembles a conventional nanostar that has been truncated near its midsection. Simulations of plasmonic properties of this geometry reveal that such structures can exhibit maximum near-field intensities that are as much as seven-times greater than the standard nanostar geometry, a finding that is corroborated by surface-enhanced Raman scattering (SERS) measurements showing large enhancement factors. The study adds nanostars to the library of nanostructure geometries that are amenable to large-area periodic arrays and provides a potential pathway for the nanofabrication of SERS substrates with even greater enhancements.  more » « less
Award ID(s):
1803917 1709881
NSF-PAR ID:
10189516
Author(s) / Creator(s):
; ; ; ; ; ;
Date Published:
Journal Name:
Nanoscale
Volume:
12
Issue:
31
ISSN:
2040-3364
Page Range / eLocation ID:
16489 to 16500
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ( , Journal of Raman Spectroscopy)
    Abstract

    The impact of tunable morphologies and plasmonic properties of gold nanostars is evaluated for the surface‐enhanced Raman scattering (SERS) detection of uranyl. To do so, gold nanostars are synthesized with varying concentrations of the Good's buffer reagent, 2‐[4‐(2‐hydroxyethyl)‐1‐piperazinyl]propanesulfonic acid (EPPS). EPPS plays three roles including as a reducing agent for nanostar nucleation and growth, as a nanostar‐stabilizing agent for solution phase stability, and as a coordinating ligand for the capture of uranyl. The resulting nanostructures exhibit localized surface plasmon resonance (LSPR) spectra that contain two visible and one near‐infrared plasmonic modes. All three optical features arise from synergistic coupling between the nanostar core and branches. The tunability of these optical resonances is correlated with nanostar morphology through careful transmission electron microscopy (TEM) analysis. As the EPPS concentration used during synthesis increases, both the length and aspect ratio of the branches increase. This causes the two lower energy extinction features to grow in magnitude and become ideal for the SERS detection of uranyl. Finally, uranyl binds to the gold nanostar surface directly and via sulfonate coordination. Changes in the uranyl signal are directly correlated to the plasmonic properties associated with the nanostar branches. Overall, this work highlights the synergistic importance of nanostar morphology and plasmonic properties for the SERS detection of small molecules.

     
    more » « less
  2. ; ; ; ; ; ; ; ; ; ; et al ( , Small)
    Abstract

    The advancement of nanoenabled wafer‐based devices requires the establishment of core competencies related to the deterministic positioning of nanometric building blocks over large areas. Within this realm, plasmonic single‐crystal gold nanotriangles represent one of the most attractive nanoscale components but where the formation of addressable arrays at scale has heretofore proven impracticable. Herein, a benchtop process is presented for the formation of large‐area periodic arrays of gold nanotriangles. The devised growth pathway sees the formation of an array of defect‐laden seeds using lithographic and vapor‐phase assembly processes followed by their placement in a growth solution promoting planar growth and threefold symmetric side‐faceting. The nanotriangles formed in this high‐yield synthesis distinguish themselves in that they are epitaxially aligned with the underlying substrate, grown to thicknesses that are not readily obtainable in colloidal syntheses, and present atomically flat pristine surfaces exhibiting gold atoms with a close‐packed structure. As such, they express crisp and unambiguous plasmonic modes and form photoactive surfaces with highly tunable and readily modeled plasmon resonances. The devised methods, hence, advance the integration of single‐crystal gold nanotriangles into device platforms and provide an overall fabrication strategy that is adaptable to other nanomaterials.

     
    more » « less
  3. ; ; ; ; ; ; ; ; ( , Advanced Materials)
    Abstract

    2D freestanding nanocrystal superlattices represent a new class of advanced metamaterials in that they can integrate mechanical flexibility with novel optical, electrical, plasmonic, and magnetic properties into one multifunctional system. The freestanding 2D superlattices reported to date are typically constructed from symmetrical constituent building blocks, which have identical structural and functional properties on both sides. Here, a general ligand symmetry‐breaking strategy is reported to grow 2D Janus gold nanocrystal superlattice sheets with nanocube morphology on one side yet with nanostar on the opposite side. Such asymmetric metallic structures lead to distinct wetting and optical properties as well as surface‐enhanced Raman scattering (SERS) effects. In particular, the SERS enhancement of the nanocube side is about 20‐fold of that of the nanostar side, likely due to the combined “hot spot + lightening‐rod” effects. This is nearly 700‐fold of SERS enhancement as compared with the symmetric nanocube superlattices without Janus structures.

     
    more » « less
  4. ; ; ; ( , Journal of Food Science)
    Abstract

    In recent years, concerns have been raised regarding the contamination of grapes with pesticide residues. As consumer demand for safer food products grows, regular monitoring of pesticide residues in food has become essential. This study sought to develop a rapid and sensitive technique for detecting two specific pesticides (phosmet and paraquat) present on the grape surface using the surface‐enhanced Raman spectroscopy (SERS) method. Gold nanostars (AuNS) particles were synthesized, featuring spiky tips that act as hot spots for localized surface plasmon resonance, thereby enhancing Raman signals. Additionally, the roughened surface of AuNS increases the surface area, resulting in improved interactions between the substrate and analyte molecules. Prominent Raman peaks of mixed contaminants were acquired and used to characterize and quantify the pesticides. It was observed that the SERS intensity of the Raman peaks changed in proportion to the concentration ratio of phosmet and paraquat. Moreover, AuNS exhibited superior SERS enhancement compared to gold nanoparticles. The results demonstrate that the lowest detectable concentration for both pesticides on grape surfaces is 0.5 mg/kg. These findings suggest that SERS coupled with AuNS constitutes a practical and promising approach for detecting and quantifying trace contaminants in food.

     Practical Application

    This research established a novel surface‐enhanced Raman spectroscopy (SERS) method coupled with a simplified extraction protocol and gold nanostar substrates to detect trace levels of pesticides in fresh produce. The detection limits meet the maximum residue limits set by the EPA. This substrate has great potential for rapid measurements of chemical contaminants in foods.

     
    more » « less
  5. ; ; ; ; ; ; ( , Nanoscale Advances)
    Confining and controlling light in extreme subwavelength scales are tantalizing tasks. In this work, we report a study of individual plasmonic film-coupled nanostar resonators where polarized plasmonic optical modes are trapped in ultrasmall volumes. Individual gold nanostars, separated from a flat gold film by a thin dielectric spacer layer, exhibit a strong light confinement between the sub-10 nm volume of the nanostar's tips and the film. Through dark field scattering measurements of many individual nanostars, a statistical observation of the scattered spectra is obtained and compared with extensive simulation data to reveal the origins of the resonant peaks. We observe that an individual nanostar on a flat gold film can result in a resonant spectrum with single, double or multiple peaks. Further, these resonant peaks are strongly polarized under white light illumination. Our simulation data revealed that the resonant spectrum of an individual film-coupled nanostar resonator is related to the symmetry of the nanostar, as well as the orientation of the nanostar relative to its placement on the gold substrate. Our results demonstrate a simple new method to create an ultrasmall mode volume and polarization sensitive plasmonic platform which could be useful for applications in sensing or enhanced light–matter interactions. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email