Electrically Controlled Enrichment of Analyte for Ultrasensitive SERS-Based Plasmonic Sensors.

Recently, sensors using surface-enhanced Raman scattering (SERS) detectors combined with superhydrophobic/superhydrophilic analyte concentration systems showed the ability to reach detection limits below the femto-molar level. However, a further increase in the sensitivity of these sensors is limited by the impossibility of the concentration systems to deposit the analyte on an area of less than 0.01 mm2. This article proposes a fundamentally new approach to the analyte enrichment, based on the effect of non-uniform electrostatic field on the evaporating droplet. This approach, combined with the optimized geometry of a superhydrophobic/superhydrophilic concentration system allows more than a six-fold reduction of the deposition area. Potentially, this makes it possible to improve the detection limit of the plasmonic sensors by the same factor, bringing it down to the attomolar level.

Ultrasensitive SERS-Based Plasmonic Sensor with Analyte Enrichment System Produced by Direct Laser Writing.

We report an easy-to-implement device for surface-enhanced Raman scattering (SERS)-based detection of various analytes dissolved in water droplets at trace concentrations. The device combines an analyte-enrichment system and SERS-active sensor site, both produced via inexpensive and high-performance direct femtosecond (fs)-laser printing. Fabricated on a surface of water-repellent polytetrafluoroethylene substrate as an arrangement of micropillars, the analyte-enrichment system supports evaporating water droplet in the Cassie-Baxter superhydrophobic state, thus ensuring delivery of the dissolved analyte molecules towards the hydrophilic SERS-active site. The efficient pre-concentration of the analyte onto the sensor site based on densely arranged spiky plasmonic nanotextures results in its subsequent label-free identification by means of SERS spectroscopy. Using the proposed device, we demonstrate reliable SERS-based fingerprinting of various analytes, including common organic dyes and medical drugs at ppb concentrations. The proposed device is believed to find applications in various areas, including label-free environmental monitoring, medical diagnostics, and forensics.