Gold Nanoring Arrays Research Articles

Tunable Gold Nanoring Arrays by Electrodeposition

AbstractGold has many exciting properties that justify its use in a wide range of applications. While gold nanoparticles are frequently used, nanorings offer an interesting new geometry. Unfortunately, few technologies exist to fabricate nanorings, which are often created by multistep lithographic methods. Furthermore, nanoring arrays are even more difficult to achieve. Herein, a one‐step, one‐pot electrodeposition method to realize arrays of gold nanorings with tunable parameters is demonstrated. It is shown that the electrodeposition of gold nanoring arrays can be easily achieved when one submerges a water droplet containing HAuCl4 into an oil‐phase containing a quaternary ammonium salt. These conditions allow for the spontaneous emulsification at the water|oil interface. The nanorings can be deposited at the edges of the emulsion droplets that become adsorbed to the electrode. Changing the concentrations of species, submersion time, and electrodeposition parameters allows us to tune relevant parameters of the array of nanorings, including the thickness and size of the rings.

Readily tunable surface plasmon resonances in gold nanoring arrays fabricated using lateral electrodeposition.

Generation and fine-tuning of surface plasmon resonances is a prerequstite for several established and emerging applications such as photovoltaics, photocatalysis, photothermal therapy, surface-enhanced spectroscopy, sensing, superlensing and lasing. We present a low-cost and scalable lateral electrodeposition method for fabrication of high aspect ratio gold nanoring arrays that exhibit multiple surface plasmon resonances in the visible to near-infrared region. Nickel disc arrays of 2 µm size were initially fabricated using maskless lithography and e-beam evaporation. Selective electrodeposition of gold on the lateral surfaces of nickel disc arrays was achieved using a 50 nm SiO2 film as an insulating mask. Growing from miniscule 100 nm wide lateral surfaces of nickel discs, nanorings with height up to 1084 nm could be obtained with their thickness and aspect ratio governed by the duration of electrodeposition. Facile tuning of the number of plasmon resonances, their resonant wavelength and relative intensity is demonstrated with applications in plasmon mediated photocatalysis and surface-enhanced Raman scattering.

Au nanoring arrays with tunable morphological features and plasmonic resonances

Gold nanoring arrays are widely applied in various fields benefitting from their localized surface plasmon resonance (LSPR) properties. A key advantage of gold nanoring arrays is that the dipole resonance peak can be systematically tuned by changing the dimensions of gold nanoring arrays. However, most of the currently reported methods for preparing gold nanoring arrays cannot conveniently control the heights of the nanorings at a low cost. Here we introduce a facile method for preparing gold nanoring arrays with tunable plasmonic resonances using colloidal lithography. The dimensions of the nanorings including diameters, lattice constants, even the heights of the nanorings can be conveniently varied. Fourier transform near-infrared (FT-NIR) absorption spectroscopy was used to obtain the plasmonic resonance spectra of the nanoring arrays. All the prepared gold nanoring arrays exhibited a strong NIR or infrared (IR) plasmonic resonance which can be tuned by varying the nanoring dimensions. This versatile method can also be used to fabricate other types of plasmonic nanostructures, such as gold nanocone arrays. The obtained gold nanoring arrays as well as nanocone arrays may have potential applications in surface-enhanced spectroscopy or plasmonic sensing.

Au nanoring arrays as surface enhanced Raman spectroscopy substrate for chemical component study of individual atmospheric aerosol particle

Monolayer-ordered gold nanoring arrays were prepared by ion-sputtering method and used as surface enhanced Raman spectroscopy (SERS) substrates to test the individual atmospheric aerosols particle. Compared to other methods used for testing atmospheric aerosols particles, the collection and subsequent detection in our work is performed directly on the gold nanoring SERS substrate without any treatment of the analyte. The SERS performance can be tuned by changing the depth of the gold nanoring cavity as originating from coupling of dipolar modes at the inner and outer surfaces of the nanorings. The electric field exhibits uniform enhancement and polarization in the ordered Au nanoring substrate, which can improve the accuracy for detecting atmospheric aerosol particles. Combined with Raman mapping, the information about chemical composition of individual atmospheric aerosols particle and distribution of specific components can be presented visually. The results show the potential of SERS in enabling improved analysis of aerosol particle chemical composition, mixing state, and other related physicochemical properties.

Polymer-assisted fabrication of gold nanoring arrays

In this paper, we report a new strategy for the fabrication of gold nanoring arrays via colloidal lithography and polymer-assisted self-assembly of gold nanoparticles (Au NPs). First, multi-segmented polymer nanorod arrays were fabricated via colloidal lithography. They were then used as templates for Au NP adsorption, which resulted in nanoparticles on the poly(4-vinyl pyridine) (P4VP) segments. Continuous gold nanorings were formed after electroless deposition of gold. The diameter, quantity, and spacing of the gold nanorings could be tuned. Three dimensional coaxial gold nanorings with varying diameters could be fabricated on a polymer nanorod by modifying the etch parameters. The nanorings exhibited optical plasmonic resonances at theoretically predicted wavelengths. In addition, the polymer-assisted gold nanorings were released from the substrate to generate a high yield of free-standing nanorings. This simple, versatile method was also used to prepare nanorings from other metals such as palladium.

Design of a quartz crystal with transparent electrode used for both QCM-D and LSPR technology

This article presents an efficient method for the design of a sensor combining localized surface plasmon resonance (LSPR) sensing with quartz crystal microbalance with dissipation monitoring (QCM-D). The sensor uses a quartz crystal coated with 7 mm radium transparent indium tin oxide (ITO) top electrode and 6 mm radium gold bottom electrode. An array of gold nanorings is fabricated on the surface of ITO electrode. The gold nanoring arrays cause 12.11 Hz frequency shift which is very small compared with 5 MHz resonance frequency. The mass sensitivity profiles of various types of “n-m” electrode sensors are compared using MATLAB and the results show that the “7-6” is more sensitive than others. Finite element modeling in ANSYS shows good sensitivity to low relative permittivity in range from 1 to 10.

Top-up fabrication of gold nanorings.

A simple method for the fabrication of gold nanorings with reliable material composition and reproducible morphology that relies on a combination of top-down and bottom-up techniques is presented. Here, lithographically defined hole arrays are used as templates for the deposition of gold nanoparticles. The resulting gold nanoparticle rings are joined by electroless deposition of gold, thereby leading to the formation of gold nanoring arrays that show plasmonic resonance in their optical spectra at theoretically predicted wavelengths. In addition, the gold nanorings can be released from the template by extensive rinsing with water, thereby enabling their further functionalization or assembly and the re-use of the template for the preparation of more nanorings.

Gold Nanoring Arrays for Near Infrared Plasmonic Biosensing

Gold nanoring array surfaces that exhibit strong localized surface plasmon resonances (LSPR) at near infrared (NIR) wavelengths from 1.1 to 1.6 μm were used as highly sensitive real-time refractive index biosensors. Arrays of gold nanorings with tunable diameter, width, and spacing were created by the nanoscale electrodeposition of gold nanorings onto lithographically patterned nanohole array conductive surfaces over large areas (square centimeters). The bulk refractive index sensitivity of the gold nanoring arrays was determined to be up to 3,780 cm−1/refractive index unit by monitoring shifts in the LSPR peak by FT-NIR transmittance spectroscopy measurements. As a first application, the surface polymerization reaction of dopamine to form polydopamine thin films on the nanoring sensor surface from aqueous solution was monitored with the real-time LSPR peak shift measurements. To demonstrate the utility of the gold nanoring arrays for LSPR biosensing, the hybridization adsorption of DNA-functionalized gold nanoparticles onto complementary DNA-functionalized gold nanoring arrays was monitored. The adsorption of DNA-modified gold nanoparticles onto nanoring arrays modified with mixed DNA monolayers that contained only 0.5 % complementary DNA was also detected; this relative surface coverage corresponds to the detection of DNA by hybridization adsorption from a 50 pM solution.

Optimization of gold nanoring arrays for biosensing in the fiber-optic communication window

To improve the limit of detection in a nanoplasmonic sensor system, the optical performance of the metal nanostructures should be optimized according to the best spectral window of the measurement instrument. We propose that the spectral window from 1460 to 1610 nm can potentially provide ultrahigh instrumental resolution for biosensing. We optimized gold nanoring arrays such that the extinction peak position is inside the proposed window, the extinction peak is sharp enough to track the peak shift with high resolution and the figure of merit (sensitivity/linewidth) of the array is optimized at the same time. The peak-sharpening effect of the array caused by coherent interaction plays a central role in the optimization. The optimized array has a lattice constant in the range [1000 nm,1060 nm], a bulk index sensitivity of around 450 nm/RIU and a figure of merit larger than 4. It is an enabling sensor element for a near-infrared sensor chip with ultrahigh resolution.

The Influences of Cooperative Swelling and Coordination on Patterned Decoration of Gold on Block Copolymer Nanospheres

Ordered nanoring arrays are a new pattern of block copolymer thin films generated by spin‐coating of block copolymer reverse micelles on silicon substrates, which can further direct the formation of gold nanoring arrays on block copolymer thin films. Here, it is reported that the cooperation of swelling and coordination can influence the surface pattern of the block copolymer nanospheres. A hexagonally arranged dot pattern can be transformed into a ring pattern on polystyrene‐block‐poly(2‐vinylpyridine) nanospheres, and the new pattern can further direct the decoration of gold nanoparticles by balancing the swelling of the poly(2‐vinylpyridine) chains and the coordination effect between gold ions and the pyridine units. image

Plasmonic nano-ring arrays through patterning gold nanoparticles into interferograms

Large-area gold nanoring arrays were fabricated using interference lithography and metallic transformation through annealing of colloidal gold nanoparticles. The strong surface tension of the suspension solution and the molten gold, as well as the effective distance of these interaction mechanisms, is responsible for the creation of gold nanorings. The size and shape of the gold nanorings can be controlled by adjusting the size of the holes in the template photoresist grating, which is accomplished in the stage of interference lithography. Furthermore, the concentration of the colloidal gold nanoparticles and the annealing temperature can be utilized to achieve further optimization of the gold nanoring structures. Optical spectroscopic measurements show unique plasmonic response of the nanoring arrays in the visible and in the infrared spectral ranges, which agrees well with the theoretical simulation. This fabrication method provides a simple and low-cost route for achieving metallic nanoring arrays in a large scale for practical applications.

Slab Thickness Dependence of Localized Surface Plasmon Resonance Behavior in Gold Nanorings

We present detailed experimental and numerical studies of plasmonic properties of gold nanoring (NR) arrays with different slab thicknesses from 15 to 125 nm. The hybrid plasmon resonances for the bonding and antibonding modes in gold NRs exhibit a high slab thickness dependence behavior in optical properties. For the thinner slab thickness below 50 nm, both hybrid modes show large spectral tunabilities by varying the slab thickness. Furthermore, for such hollow NR structure, the enhancements of electric field intensities at the inner and outer ring surfaces when reducing the slab thickness are investigated. We observe a significant transition of field distributions for the antibonding mode. All these features can be understood by surface charge distributions from our simulations. The results of this study offer a potential strategy to design a composite plasmonic nanostructure with large field enhancement for numerous applications.

Lithographically Patterned Electrodeposition of Gold, Silver, and Nickel Nanoring Arrays with Widely Tunable Near-Infrared Plasmonic Resonances

A novel low-cost nanoring array fabrication method that combines the process of lithographically patterned nanoscale electrodeposition (LPNE) with colloidal lithography is described. Nanoring array fabrication was accomplished in three steps: (i) a thin (70 nm) sacrificial nickel or silver film was first vapor-deposited onto a plasma-etched packed colloidal monolayer; (ii) the polymer colloids were removed from the surface, a thin film of positive photoresist was applied, and a backside exposure of the photoresist was used to create a nanohole electrode array; (iii) this array of nanoscale cylindrical electrodes was then used for the electrodeposition of gold, silver, or nickel nanorings. Removal of the photoresist and sacrificial metal film yielded a nanoring array in which all of the nanoring dimensions were set independently: the inter-ring spacing was fixed by the colloidal radius, the radius of the nanorings was controlled by the plasma etching process, and the width of the nanorings was controlled by the electrodeposition process. A combination of scanning electron microscopy (SEM) measurements and Fourier transform near-infrared (FT-NIR) absorption spectroscopy were used to characterize the nanoring arrays. Nanoring arrays with radii from 200 to 400 nm exhibited a single strong NIR plasmonic resonance with an absorption maximum wavelength that varied linearly from 1.25 to 3.33 μm as predicted by a simple standing wave model linear antenna theory. This simple yet versatile nanoring array fabrication method was also used to electrodeposit concentric double gold nanoring arrays that exhibited multiple NIR plasmonic resonances.

Gold nanoring arrays from responsive block copolymer templates

We report a pH-mediated synthetic route for the production of ordered and size-tuneable arrays of gold nanorings using responsive block copolymer micelles as templates.

Two-dimensional nanotriangle and nanoring arrays on silicon wafer

Gold and tungsten were deposited on silicon wafer and/or glass substrates by using random incidence sputtering deposition and thermal vapor deposition techniques. Two-dimensional tungsten nanotriangle and gold nanoring arrays were obtained on the silicon wafer substrate and examined using scanning electron microscope and atomic force microscope analysis. The size of the equal tungsten nanotriangles is within 100 nm per side and 210 nm apart from each other. The size of gold nanorings is 220 nm diameter, 40 nm wide, 10 nm thick, and 560 nm apart from each other. No nanorings were found on the glass substrate. Mechanisms for the formation of nanoring arrays are discussed.