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Ultrafast Laser-Ablated Nanoparticles and Nanostructures for Surface-Enhanced Raman Scattering-Based Sensing Applications

The technique of ultrafast laser ablation in liquids has evolved and matured over the past decade, with several impending applications in various fields ...

University of Hyderabad

Surface enhanced Raman spectroscopy (SERS) is a cutting edge analytical tool for trace analyte detection due to its highly sensitive, non-destructive and fingerprinting capability. Herein, we report the detection of multiple analytes from various mixtures using gold nanoparticles (NPs) and nanostructures (NSs) as SERS platforms. NPs and NSs were achieved through the simple approach of laser ablation in liquids (LAL) and their morphological studies were conducted with a UV-Visible absorption spectrometer, a high resolution transmission electron microscope (HRTEM) and a field emission scanning electron microscope (FESEM). The fabricated NPs/NSs allowed the sensitive and selective detection of different mixed compounds containing (i) rhodamine 6G (Rh6G) and methylene blue (MB), (ii) crystal violet (CV) and malachite green (MG), (iii) picric acid (explosive) and MB (dye), (iv) picric acid and 3-nitro-1,2,4- triazol-5-one (explosive, NTO) and (v) picric acid and 2,4-dinitrotoluene (explosive, DNT) using a portable Raman spectrometer. Thus, the obtained results demonstrate the capability of fabricated SERS substrates in identifying explosives and dyes from various mixtures. This could pave a new way for simultaneous detection of multiple analytes in real field applications.

SERS based detection of multiple analytes from dye/explosive mixtures using picosecond laser fabricated gold nanoparticles and nanostructures.

Fabrication of reproducible and versatile surface-enhanced Raman scattering (SERS) substrates is crucial for real-time applications such as explosive detection for human safety and biological imaging for cancer diagnosis. However, it still remains a challenging task, even after several methodologies were developed by various research groups, primarily due to (a) a lack of consistency in detection of a variety of molecules (b) cost-effectiveness of the SERS substrates prepared, and (c) byzantine preparation procedures, etc. Herein, we establish a procedure for preparing reproducible SERS-active substrates comprised of laser-induced nanoparticle-embedded periodic surface structures (LINEPSS) and metallization of silicon (Si) LINEPSS. LINEPSS were fabricated using the technique of femtosecond laser ablation of Si in acetone. The versatile SERS-active substrates were then achieved by two ways, including the drop casting of silver (Ag)/gold (Au) nanoparticles (NPs) on Si LINEPSS and Ag plating on the Si LINEPSS structures. By controlling the LINEPSS grating periodicity, the effect of plasmonic nanoparticles/plasmonic plating on the Si NPs embedded periodic surface structures enormously improved the SPR strength, resulting in the consistent and superior Raman enhancements. The reproducible SERS signals were achieved by detecting the molecules of Methylene Blue (MB), 2,4-dinitrotoluene (DNT), and 5-amino-3-nitro-l,2,4-triazole (ANTA). The SERS signal strength is determined by the grating periodicity, which, in turn, is determined by the input laser fluence. The SERS-active platform with grating periodicity of 130 ± 10 nm and 150 ± 5 nm exhibited strong Raman enhancements of ∼10 for MB and ∼10 for ANTA molecules, respectively, and these platforms are demonstrated to be capable, even for multiple usages.

Femtosecond Laser-Induced, Nanoparticle-Embedded Periodic Surface Structures on Crystalline Silicon for Reproducible and Multi-utility SERS Platforms.

We present a systematic study on the fabrication, characterization of versatile, and low-cost filter paper-based surface-enhanced Raman spectroscopy (SERS) substrates loaded with salt-induced aggregated Ag/Au nanoparticles (NPs). These were demonstrated as efficient SERS substrates for the detection of multiple explosive molecules such as picric acid (5 μM), 2,4-dinitrotoluene (1 μM), and 3-nitro-1,2,4-triazol-5-one (10 μM) along with a common dye molecule (methylene blue, 5 nM). The concentrations of the dye and explosive molecules in terms of mass represent 31.98 pg, 11.45 ng, 1.82 ng, and 13.06 ng, respectively. Silver (Ag) and gold (Au) colloidal NPs were prepared by femtosecond laser (∼50 fs, 800 nm, 1 kHz) ablation of Ag/Au-target immersed in distilled water. Subsequently, the aggregated nanoparticles were achieved by mixing the pure Ag and Au NPs with different concentrations of NaCl. These aggregated NPs were characterized by UV-visible absorption and high-resolution transmission electron microscopy techniques. The SERS substrates were prepared by soaking the filter paper in aggregated NPs. The morphologies of the paper substrates were investigated using field-emission scanning electron microscopy technique. We have achieved superior enhancements with high reproducibility and sensitivity for filter paper substrates loaded with Ag/Au NPs mixed for an optimum concentration of 50 mM NaCl.

Ag/Au Nanoparticle-Loaded Paper-Based Versatile Surface-Enhanced Raman Spectroscopy Substrates for Multiple Explosives Detection.

We demonstrate an ultrafast laser-ablated hierarchically patterned silver nanoparticle/graphene oxide (AgNP/GO) hybrid surface-enhanced Raman scattering (SERS) substrate for highly sensitive and reproducible detection of an explosive marker 2,4-dinitrotoluene (2,4-DNT). A hierarchical laser-patterned silver sheet (Ag-S) is achieved by ultrafast laser ablation in air with pulse energies of 25, 50, and 100 μJ. Multiple laser pulses at a wavelength of 800 nm and a pulse repetition rate of 50 fs at 1 kHz are directly focused on Ag-S to produce and deposit AgNPs onto Ag-S. The surface morphology of ablated Ag-S was evaluated using atomic force microscopy, optical profilometry, and field emission scanning electron microscopy (FESEM). A rapid increase in the ablation rate with increasing laser energy was observed. Selected area Raman mapping is performed to understand the intensity and size distribution of AgNPs on Ag-S. Further, GO was spin-coated onto the AgNPs produced by ultrafast ablation on Ag-S. The hierarchical laser-patterned AgNP/GO hybrid structure was characterized using FESEM, high-resolution transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and Raman spectroscopy. Further, hierarchical laser-patterned AgNP/GO hybrid structures have been utilized as SERS-active substrates for the selective detection of 2,4-DNT, an explosive marker. The developed SERS-active sensor shows good stability and high sensitivity up to picomolar (pM) concentration range with a Raman intensity enhancement of ∼10 for 2,4-DNT. The realized enhancement of SERS intensity is due to the cumulative effect of GO coated on Ag-S as a proactive layer and AgNPs produced by ultrafast ablation.

Hierarchical Laser-Patterned Silver/Graphene Oxide Hybrid SERS Sensor for Explosive Detection.

The development of recyclable surface enhanced Raman scattering (SERS) based sensors has been in huge demand for trace level explosives detection. A simple, hybrid Silicon (Si) nanotextured target-based SERS platform is fabricated through patterning micro square arrays (MSA) on Si using femtosecond (fs) laser ablation technique at different fluences. Using the hybrid target Si MSA substrate loaded/decorated with Ag-Au alloy NPs (obtained using femtosecond ablation in liquids) we demonstrate the trace level detection of organic nitro-explosives [picric acid (PA), 2,4-dinitrotoluene (DNT), and 1, 3, 5-trinitroperhydro-1, 3, 5-triazine (RDX)] and their mixtures. The microstructures/nanostructures of MSA fabricated at an input fluence of 9.55 J/cm, and decorated with Ag-Au alloy NPs, exhibited exceptional SERS enhancement factors (EFs) up to ∼10 for MB, ∼10 for PA, and ∼10 for RDX with the detection limits obtained being ∼5 pM, ∼36 nM, and ∼400 nM for MB, PA and RDX respectively. Furthermore, we demonstrate these SERS substrates possess good reproducibility (RSD values < 15%) and a superior performance compared to a commercial Ag substrate (SERSitive, Poland). Three binary mixtures, i.e. MB-PA, MB-DNT, PA-DNT at different concentrations, were also investigated using the same SERS substrate to test the efficacy. Further, the SERS spectra of dyes, explosives, and complex mixtures were utilized for discrimination/classification using principal component analysis.

Instantaneous trace detection of nitro-explosives and mixtures with nanotextured silicon decorated with Ag-Au alloy nanoparticles using the SERS technique.

We report the fabrication and performance evaluation of hybrid surface-enhanced Raman scattering (SERS) substrates involving laser ablation and chemical routes for the trace-level detection of various analyte molecules. Initially, picosecond laser ablation experiments under ambient conditions were performed on pure silver (Ag) and gold (Au) substrates to achieve distinct nanosized features on the surface. The properties of the generated surface features on laser-processed portions of Ag/Au targets were systematically analyzed using UV-visible reflection and field emission scanning electron microscopy studies. Later, hybrid-SERS substrates were achieved by grafting the chemically synthesized Au nanostars on the plain and laser-processed plasmonic targets. Subsequently, we employed these as SERS platforms for the detection of a pesticide (thiram), a molecule used in explosive compositions [ammonium nitrate (AN)], and a dye molecule [Nile blue (NB)]. A comparative SERS study between the Au nanostar-decorated bare glass, silicon, Ag, Au, and laser-processed Ag and Au targets has been established. Our studies and the obtained data have unambiguously determined that laser-processed Ag structures have demonstrated reasonably good enhancements in the Raman signal intensities for distinct analytes among other substrates. Importantly, the fabricated hybrid SERS substrate of "Au nanostar-decorated laser-processed Ag" exhibited up to eight times enhancement in the SERS intensity compared to laser-processed Ag (without nanostars), as well as up to three times enhancement than the Au nanostar-loaded plain Ag substrates. Additionally, the achieved detection limits from the Au nanostar-decorated laser-processed Ag SERS substrate were ∼50 pM, ∼5 nM, and ∼5 μM for NB, thiram, and AN, respectively. The estimated enhancement factors accomplished from the Au nanostar-decorated laser-processed Ag substrate were ∼10, ∼10, and ∼10 for NB, thiram, and AN, respectively.

Hybrid Surface-Enhanced Raman Scattering Substrates for the Trace Detection of Ammonium Nitrate, Thiram, and Nile Blue.

Recently, filter paper (FP)-based surface-enhanced Raman scattering (SERS) substrates have stimulated significant attention owing to their promising advantages such as being low-cost, easy to handle, and practically suitable for real-field applications in comparison to the solid-based substrates. Herein, a simple and versatile approach of laser-ablation in liquid for the fabrication of silver (Ag)-gold (Au) alloy nanoparticles (NPs). Next, the optimization of flexible base substrate (sandpaper, printing paper, and FP) and the FP the soaking time (5−60 min) was studied. Further, the optimized FP with 30 min-soaked SERS sensors were exploited to detect minuscule concentrations of pesticide (thiram-50 nM), dye (Nile blue-5 nM), and an explosive (RDX-1,3,5-Trinitroperhydro-1,3,5-triazine-100 nM) molecule. Interestingly, a prominent SERS effect was observed from the Au NPs exhibiting satisfactory reproducibility in the SERS signals over ~1 cm2 area for all of the molecules inspected with enhancement factors of ~105 and relative standard deviation values of <15%. Furthermore, traces of pesticide residues on the surface of a banana and RDX on the glass slide were swabbed with the optimized FP substrate and successfully recorded the SERS spectra using a portable Raman spectrometer. This signifies the great potential application of such low-cost, flexible substrates in the future real-life fields.

Picosecond Laser-Ablated Nanoparticles Loaded Filter Paper for SERS-Based Trace Detection of Thiram, 1,3,5-Trinitroperhydro-1,3,5-triazine (RDX), and Nile Blue.

We have developed simple and cost-effective surface-enhanced Raman scattering (SERS) substrates for the trace detection of pesticide (thiram and thiabendazole) and dye (methylene blue and Nile blue) molecules. Surface patterns (micro/nanostructures) on silicon (Si) substrates were fabricated using the technique of femtosecond (fs) laser ablation in ambient air. Different surface patterns were achieved by tuning the number of laser pulses per unit area (4200, 8400, 42 000, and 84 000 pulses per mm) on Si. Subsequently, chemically synthesized gold (Au) nanostars were embedded in these laser-patterned areas of Si to achieve a plasmonic active hybrid SERS substrate. Further, the SERS performance of the as-prepared Au nanostar embedded Si substrates were tested with different probe molecules. The as-prepared substrates allowed us to detect a minimum concentration of 0.1 ppm in the case of thiram, 1 ppm in the case of thiabendazole (TBZ), 1.6 ppb in the case of methylene blue (MB), and 1.8 ppb in case of Nile blue (NB). All these were achieved using a simple, field-deployable, portable Raman spectrometer. Additionally, the optimized SERS substrate demonstrated ∼21 times higher SERS enhancement than the Au nanostar embedded plain Si substrate. Furthermore, the optimized SERS platform was utilized to detect a mixture of dyes (MB + NB) and pesticides (thiram + TBZ). The possible reasons for the observed additional enhancement are elucidated.

Sree Satya Bharati Moram

Advanced Centre for Research in High Energy Materials (ACRHEM),
DRDO Industry Academia - Centre of Excellence (DIA-COE),
Advanced Centre for Research in High Energy Materials (ACRHEM), DRDO Industry Academia - Centre of Excellence (DIA-COE)

University of Hyderabad

Ultrafast Laser-Ablated Nanoparticles and Nanostructures for Surface-Enhanced Raman Scattering-Based Sensing Applications