This paper presents a cost-effective approach for the template-assisted electrodeposition fabrication of substrates for surface-enhanced Raman scattering (SERS) with metal nanowires (NWs) grown in pores of polymer track-etched membranes (TM). This technique allows the synthesis of NWs array with its certain surface density and diameter (from dozen to hundreds of nm). NWs length also may be varied (order of μm) by controlling deposition time. Here we grow vertical Ag-NWs which are leaning towards their nearest neighbors, forming self-assembled bundles whose parameters depend on the NW aspect ratio (length to diameter). We show that in such bundles there are “hot spots” in the nm-gaps between NWs tips. Computer simulations have demonstrated a strong enhancement of the electric field within these hot spots; thus, the Raman signal is markedly amplified for analyte molecules placed directly inside the gaps. We have experimentally proved the potential of this SERS-technique on the example of 4-Mercaptophenylboronic acid (4-MPBA). For 4-MPBA the maximal enhancement of Raman signal was found at NWs length of ~1.6 μm and diameter of ~100 nm. The effect is higher (up to twice) if “wet” substrate is used just immediately after the TM polymer removal so that the tips are brought to lean after analyte exposure. We suggest this new type of nanostructured SERS-substrates as a base of effective sensing of extremely low concentration of analytes.
1 December 2020 in Bulletin of the Russian Academy of Sciences: Physics
A procedure is proposed for template-assisted synthesis on track membranes using iodide electrolyte to produce substrates with dendritic nanostructures for
The most relevant technique for portable (on-chip) sensors is Surface Enhanced Raman Scattering (SERS). This strategy crashes in the case of large (biorelevant) molecules and nano-objects, whose SERS spectra are irreproducible for “homeopathic” concentrations. We suggested solving this problem by SERS-mapping. We analyzed the distributions of SERS parameters for relatively “small” (malachite green (MG)) and “large” (phthalocyanine, H2Pc*) molecules. While fluctuations of spectra for “small” MG were negligible, noticeable distribution of spectra was observed for “large” H2Pc*. We show that the latter is due to a random arrangement of molecules with respect to “hot spot” areas, which have limited sizes, thus amplifying the lines corresponding to vibrations of different molecule parts. We have developed a method for engineering low-cost SERS substrates optimized for the best enhancement efficiency and a measurement protocol to obtain a reliable Raman spectrum, even for a countable number of large molecules randomly distributed over the substrate.
This study presents a method for fabricating a film-based heating element using a polymer material with an array of intersecting conductive elements embedded within it. Track-etched membranes (TM) with a thickness of 10 μm were used as the template, and their pores were filled with metal, forming a three-dimensional grid. Due to the unique manufacturing process of TM, the pores inside intersect with each other, allowing for contacts between individual nanowires (NWs) when filled with metal. Experimental results demonstrated that filling the TM pores with silver allows for heating temperatures up to 78 degrees without deformation or damage to the heating element. The resulting flexible heating element can be utilized in medical devices for heating purposes or as a thermal barrier coating.
The identification of high-energy compounds in trace concentrations not only in the laboratory, but also in field conditions is of particular interest. The process should be clear, easy, and well-recognizable. We formed SERS-active substrates by using elongated nickel nanotubes synthesized by electrochemical deposition in the pores of ion-track membranes and coated them with gold for further application in the detection of low concentrations of analytes. The substrates were characterized using various techniques to determine the morphology of the nanotubes and modifying gold layer. The possibility of obtaining two types of gold-layer morphology was shown: in the form of a smooth film up to 20–50 nm thick and a coating with nanoneedles up to 250 nm long. The electric fields around the nanotubes were simulated at a laser wavelength of 532 nm to demonstrate the influence of the gold-layer morphology on the field distribution. The “needle” morphology was chosen to form the most effective SERS-active substrates for detection of low concentrations of aromatic polynitro compounds. The spectral peaks were identified by comparing the model and experimental Raman spectra at concentrations down to 10−5 M. Within this limit, all peaks (“fingerprints” of the substance) were clearly distinguishable.
A method for the formation of magneto-optical one-dimensional (1-D) nanostructures by the electrodeposition method into the pores of track-etched membranes is presented in this letter. Two possible techniques are considered: the synthesis of magnetic nanotubes and their subsequent coating with silver, as well as the synthesis of vertical-standing arrays of layered magneto-optical nanowires (NWs) with alternating layers of nickel and silver. The resulting nanotubes and NWs are polycrystalline microstructures with a nanostructured plasmon-active surface. The absorption spectra have a distinct peak corresponding to the position of the local plasmon resonance: in the near-infrared range for the nickel nanotubes coated with silver and in the optical range for the layered NWs. For layered NWs, there is a combination of absorption peaks of both silver and nickel. The use of the obtained 1-D magneto-optical nanostructures for the formation of plasmon-active magnetically controlled substrates as surface-enhanced Raman spectroscopy (SERS) active surfaces is suggested for the detection of Rhodamine 6G in concentration down to 10 –9 M. The increase of SERS signal intensity by using a magnetic field is shown for concentration 10 −3 M with an extra signal amplification of more than four times.