Albert Gutés

Silver Dendrites from Galvanic Displacement on Commercial Aluminum Foil As an Effective SERS Substrate

A silver galvanic displacement process on commercial aluminum foil has been carried out to produce cost-effective SERS substrates. The process is based on an extremely simple redox process where aluminum is oxidized while silver ions are reduced, yielding a final silver dendritic structure that offers a large surface area-to-volume ratio. XPS measurements confirmed the metallic nature of the formed dendrites. SERS substrates were fabricated by spreading of the dendrites on double side Scotch tape attached to a paper slide. Three different thiols were incubated to achieve SAM formation on the Ag dendrites and measured by Raman spectroscopy. The obtained spectra presented well resolved bands and provided valuable information regarding the orientation of the thiols. The high Raman intensity also demonstrates the high enhancement capacities of the produced silver structures. The overall method is cost-effective and allows the use of silver dendrite paste for the mass production of SERS-active substrates, including on flexible substrates and/or via screen printing.

Single-layer CVD-grown graphene decorated with metal nanoparticles as a promising biosensing platform

A new approach to the development of a single-layer graphene sensor decorated with metal nanoparticles is presented. Chemical vapor deposition is used to grow single layer graphene on copper. Decoration of the single-layer graphene is achieved by electroless deposition of Au nanoparticles using the copper substrate as a source of electrons. Transfer of the decorated single-layer graphene on glassy carbon electrodes offers a sensitive platform for biosensor development. As a proof of concept, 10 units of glucose oxidase were deposited on the surface in a Nafion matrix to stabilize the enzyme as well as to prevent interference from ascorbic acid and uric acid. Amperometric linear response calibration in the μmoll(-1) is obtained. The presented methodology enables highly sensitive platforms for biosensor development, providing a scalable roll-to-roll production with a much more reproducible scheme when compared to the graphene biosensors reported previously based on drop-cast of multi-layer graphene suspensions.

Silver nanodesert rose as a substrate for surface-enhanced Raman spectroscopy.

Silver galvanic displacement on silicon has been employed to produce large-area reproducible substrates, with morphology similar to that of the natural desert rose but on the micrometer scale. The process is based on an extremely simple wet chemistry approach using only AgF and KF, as silver and fluoride sources. A key element is the absence of HF in the deposition solution, which has been commonly used in previous silver galvanic displacement processes. The new process affords a higher degree of control in the redox reaction than those reported previously. The structures formed in this manner possess a large area-to-volume ratio with a high density of rough silver flakes uniformly distributed across the substrate. The silver morphology on the nanometer scale is shown to provide an excellent platform for surface-enhanced Raman spectroscopy (SERS), yielding detection levels for trans-1,2-bis(4-pyridyl)ethylene, 4-mercaptopyridine, and Rhodamine 6G in solution down to ppb, ppt, and ppq limits, respectively. The SERS reproducibility on the substrate was verified by monitoring the signal intensity variations across the sample. The simplicity of the substrate fabrication process, as well as the excellent uniformity, opens up opportunities for the quantitative and in-field chemical trace analysis using these substrates.

Graphitization of n-type polycrystalline silicon carbide for on-chip supercapacitor application

Synthesis of silicon carbide-derived carbon films with excellent supercapacitor characteristics is demonstrated by a process that is fully compatible with standard microfabrication technology. NiTi alloy deposited on nitrogen-doped polycrystalline SiC films is shown to result in the growth of a rough, porous, high conductivity, nanocrystalline graphitic carbon film upon rapid thermal annealing to 1050 °C. Electrodes fabricated in this manner exhibit high charge/discharge rates with a time constant of about 0.062 s. Analysis shows that the incorporated nitrogen in the carbon electrode may induce pseudo-capacitance, and the electrodes exhibit the capacitance/area values comparable to those reported on carbon nanotube-based supercapacitors.

Gold-Coated Silver Dendrites as SERS Substrates with an Improved Lifetime

Nanostructured silver is known to yield the highest signal-enhancement factors in surface-enhanced Raman spectroscopy, but its low chemical stability toward oxidation presents a challenge in the realization of Ag-based SERS substrates with long operating lifetimes. Here, a study of the long-term stability of silver dendrites as SERS substrates is reported. SERS spectra of 1,2-benzenedithiol monolayers on Ag dendrites, acquired over a period of time in excess of 1 year, shows appreciable degradation with time. However, no degradation is observed in the spectra of monolayers deposited on Ag dendrites that were coated with a monolayer-thin Au film deposited by an immersion plating process. X-ray photoelectron spectra confirm the oxidation of the uncoated Ag dendrites whereas no chemical changes are detected in the Au-coated ones. These results suggest that the galvanic displacement of Au on preformed Ag nanostructures provides a suitable route to producing SERS-active substrates with long operating and/or shelf lifetimes.

Ultrasmooth gold thin films by self-limiting galvanic displacement on silicon.

Galvanic displacement (GD), a type of electroless deposition, has been used to obtain ultrasmooth gold thin films on silicon <111>. The novel aspect of the method presented herein is the absence of fluoride ions in the liquid phase, and its principal advantage when compared to previous efforts is that the process is inherently self-limiting. The self-limiting factor is due to the fact that in the absence of fluorinated species, no silicon oxide is removed during the process. Thus, the maximum gold film thickness is achieved when elemental silicon is no longer available once the surface is oxidized completely during the galvanic displacement process. X-ray photoelectron spectroscopy has been used as a tool for thickness measurement, using the gold to silicon ratio as an analytical signal. Three gold plating solutions with different concentrations of KAuCl₄ (2, 0.2, and 0.02 mM) have been used to obtain information about the formation rate of the gold film. This XPS analysis demonstrates the formation of gold films to a maximum thickness of ∼3.5 Å. Atomic force microscopy is used to confirm surface smoothness, suggesting that the monolayer growth does not follow the Volmer-Weber growth mode, in contrast to the GD process from aqueous conditions with fluorinated species.

Single crystal silicon nanopillars, nanoneedles and nanoblades with precise positioning for massively parallel nanoscale device integration

Arrays of precisely positioned single crystal silicon nanopillars, nanoneedles, and nanoblades with minimum feature sizes as small as 30 nm are fabricated using entirely scalable top-down fabrication techniques. Using the same scalable technologies, devices consisting of electrically connected silicon nanopillars with multiple addressable electrodes for each nanostructure are realized. The arrays of nanopillars, nanoneedles, and nanoblades are shown to exhibit Raman signal enhancement on 1,2-benzenedithiol monolayers, opening a path to nanodevices that manipulate, position, detect and analyze molecules.

Graphitization of n-type polycrystalline silicon carbide and its application for micro- supercapacitors

Owing to the high power density, long life time and environmentally friendly characteristics, micro-supercapacitors have attracted much attention for powering microelectromechanical systems (MEMS) devices. This paper describes the fabrication and performance of a planar micro-supercapacitor. The fabrication process is large scale and IC compatible, and thus it can be integrated with microelectronics. The device, made of high conductivity graphitic carbon (GC) on nitrogen-doped polycrystalline 3C-SiC (poly-SiC), has very high charge/discharge rates. The incorporated nitrogen in the carbon electrode induces pseudo-capacitance and realizes nearly twice the specific capacitance value reported on carbon nanotube (CNT) supercapacitors.