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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

A new series of non-aqueous phthalocyanines having 3,4,5-trimethoxy phenyl group at peripheral positions in which the central cavity possessing Cu(II), Zn(II), and without metals has been synthesized, and its absorption, fluorescence (steady-state and excited state lifetimes), electrochemical, and third-order nonlinear optical (NLO) properties were evaluated. Absorption studies data suggest that all three phthalocyanines obey Beer-Lambert's law, and the redox properties indicate that both oxidation and reduction reactions are macrocyclic centered. The singlet quantum yields were measured in different solvents and were found to be in the range of 0.2-0.5 in the case of free-base, whereas it was in the range of 0.1-0.5 in zinc derivative, while the time-resolved fluorescence data revealed lifetimes of typically a few ns. The third-order NLO properties were investigated using the Z-scan technique with kilohertz (for retrieving true electronic nonlinearities) and megahertz repetition rate femtosecond pulses at 800 nm. Intensity-dependent Z-scan studies revealed robust NLO coefficients for solutions and thin films (two-photon absorption cross-sections of 9,300-57,000 GM) of these molecules suggesting a strong potential for optical switching, imaging, and optical limiting applications.

Optical, Electrochemical, Third-Order Nonlinear Optical Investigations of 3,4,5-Trimethoxy Phenyl Substituted Non-Aqueous Phthalocyanines.

Given the intrinsic nature of low reproducibility and signal blinking in the surface enhanced Raman scattering (SERS) technique, especially while detecting trace/ultra-trace amounts, it remains a major challenge to quantify the analyte under study. Here we present a simple and economically viable, flexible hydrophobic plasmonic filter paper-based SERS substrate for the quantification of two trace analytes [crystal violet (CV) and picric acid (PA)] using machine learning techniques and SERS data. The wettability of the substrate was modified with an easy and low-cost technique of coating it with silicone oil. Gold nanoparticles were synthesized using a femtosecond laser ablation in water technique. The prepared nanoparticles were characterized using UV, TEM, and SEM techniques and subsequently loaded onto filter papers before using them for SERS studies. We have considered the SERS intensities of the analytes at different concentrations with over 900 spectra to train the model. Principal component analysis (PCA) was used to reduce the dimensionality and, hence, the complexity of the model. Furthermore, support vector regression was used to quantify the analyte molecules and we achieved an  error of 0.9629 for CV and 0.9472 for PA. In conjunction with a portable Raman spectrometer and a computation time of less than <10 s, we believe that this is an affordable and rapid method for quantification of analytes using the SERS technique.

Machine learning for rapid quantification of trace analyte molecules using SERS and flexible plasmonic paper substrates.

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.

A zeroth-order, non-diffracting Bessel beam, generated by picosecond laser pulses (1064 nm, 10 Hz, 30 ps) through an axicon, was utilized to perform pulse energy-dependent (12 mJ, 16 mJ, 20 mJ, 24 mJ) laser ablation of silver (Ag) substrates in air. The fabrication resulted in finger-like Ag nanostructures (NSs) in the sub-200 nm domain and obtained structures were characterized using the FESEM and AFM techniques. Subsequently, we employed those Ag NSs in surface-enhanced Raman spectroscopy (SERS) studies achieving promising sensing results towards trace-level detection of six different hazardous materials (explosive molecules of picric acid (PA) and ammonium nitrate (AN), a pesticide thiram (TH) and the dye molecules of Methylene Blue (MB), Malachite Green (MG), and Nile Blue (NB)) along with a biomolecule (hen egg white lysozyme (HEWL)). The remarkably superior plasmonic behaviour exhibited by the AgNS corresponding to 16 mJ pulse ablation energy was further explored. To accomplish a real-time application-oriented understanding, time-dependent studies were performed utilizing the AgNS prepared with 16 mJ and TH molecule by collecting the SERS data periodically for up to 120 days. The coated AgNSs were prepared with optimized gold (Au) deposition, accomplishing a much lower trace detection in the case of thiram (~50 pM compared to ~50 nM achieved prior to the coating) as well as superior EF up to ~10 (~10 before Au coating). Additionally, these substrates have demonstrated superior stability compared to those obtained before Au coating.

Picosecond Bessel Beam Fabricated Pure, Gold-Coated Silver Nanostructures for Trace-Level Sensing of Multiple Explosives and Hazardous Molecules.

A series of three novel tetrabenzotriazacorroles (TBCs) designed with an alkyl substituent -butyl group (TBC-tert), an electron donor phenothiazine group (TBC-PTZ) and an energy donor carbazole group (TBC-CBZ) on the peripheral position with phosphorus metal in the cavity have been synthesized. All three compounds were characterized using various spectroscopic techniques and we assessed their femtosecond third-order nonlinear optical (NLO) properties. TBCs exhibit the properties of both phthalocyanines and corroles as they are derived from parent phthalocyanines. The optical studies revealed a new band at ∼450 nm, which was absent in the parent phthalocyanine molecules, and all three compounds obeyed Beer-Lambert's law. Singlet-state quantum yields were measured in different solvents and were found to be in the range of 0.3 to 0.6 for TBC-tert, 0.21 to 0.25 in the case of TBC-PTZ and 0.31 to 0.41 for TBC-CBZ. Time-resolved fluorescence studies revealed lifetimes in the ns regime (typically few ns). The redox properties of the TBCs suggest that they are easier to oxidize and harder to reduce and exhibit multiple oxidation and reduction potentials. Using the -scan technique, the third-order NLO properties were investigated with kilohertz and megahertz repetition rate femtosecond pulses at 800 nm. We report the first observation of strong three-photon absorption in these molecules with coefficients of ∼10 cm W (∼10 cm W) with kHz (MHz) repetition rate fs pulse excitation.

Novel phosphorus(V) tetrabenzotriazacorroles: synthesis, characterization, optical, electrochemical, and femtosecond nonlinear optical studies.

Asymmetrically substituted porphyrins possessing ethyl acetoacetate or acetylacetone (EAA or acac) with six bromine atoms at β-positions were synthesized and then characterized by various spectroscopic techniques, such as UV-Vis, fluorescence and NMR, and also by CV, DFT, MALDI-TOF-MS and elemental analysis. The mechanistic pathway followed the nucleophilic substitution reaction (nucleophile: EAA and acac) with MTPP(NO)Br (M = 2H, Cu(II), and Ni(II)), and the resultant β-heptasubstituted porphyrins exhibited keto-enol tautomerism, as supported by H NMR spectroscopy. The six bulky bromo and EAA/acac groups made the macrocyclic ring highly electron deficient and nonplanar such that the quantum yield and fluorescence intensity for HTPP[EAA]Br and HTPP[acac]Br were severely reduced in contrast to those values for HTPP. The poor electron density and nonplanarity over the porphyrin ring shifted the first oxidation potential from 11 to 521 mV anodically for MTPP[X]Br [M = 2H, Cu(II), and Ni(II); X = EAA or acac] as compared to corresponding MTPPs. Notably, density functional theory proved the nonplanarity of the synthesized porphyrins as Δ24 spans from ±0.546 to ± 0.559 Å while Δ stretches from ±0.973 to ±1.162 Å. The third-order nonlinear optical measurements were performed using the femtosecond pulsed laser -scan technique at 800 nm and 1 kHz repetition rate to acquire insights into nonlinear absorption and nonlinear refraction of the porphyrins. The three-photon absorption coefficients () are in the range of 2.2 × 10-2.8 × 10 cm W and the nonlinear refractive index values were in the range of 3.7 × 10-5.1 × 10 cm W. The higher-order nonlinear absorption exhibited by porphyrins helps improve resolution at depth for various photonic and optoelectronic applications.

Ethyl acetoacetate and acetylacetone appended hexabromo porphyrins: synthesis, spectral, electrochemical, and femtosecond third-order nonlinear optical studies.

CsAgInCl double perovskite (DP) nanocrystals (NCs) are an emerging class of materials with promising application potential in photonics/optoelectronics owing to their nontoxicity, direct bandgap, and high thermal and moisture stability. These NCs are, however, rarely explored for nonlinear optical (NLO) applications. Herein, we present a comprehensive investigation of the photophysical and nonlinear optical properties of erbium- (Er) and ytterbium (Yb)-doped CsAgInCl nanocrystals (denoted as Er-DP and Yb-DP, respectively). Temperature-dependent photoluminescence of these NCs was analyzed to estimate their exciton binding energy, Huang-Rhys parameter (), and electron-phonon coupling strength, which are of fundamental interest to gain an in-depth understanding of the material systems. Femtosecond -scan experiments with 800 nm excitation revealed the reverse saturable absorption (RSA) behavior owing to three-photon absorption (3PA). The obtained values of the 3PA coefficients were 1.35 × 10 and 1.64 × 10 cm GW, respectively, and the nonlinear refractive indices were estimated to be 1.02 × 10 and 1.15 × 10 cm W, respectively, for Er-DP and Yb-DP. These values are superior to those obtained in undoped CsAgInCl NCs. The physical parameter, Kane energy, which is closely related to the magnitude of the oscillator strength, was estimated to be 25 eV and 26 eV for Er-DP and Yb-DP, respectively. As a proof-of-concept application, we further obtained the optical limiting onset and figure of merit to reveal their prospect as an optical limiter and in photonic switching application. With such emission and nonlinear optical properties, we anticipate that lanthanide-doped CsAgInCl NCs can be used for designing eco-friendly nonlinear optoelectronic/photonic devices.

Dipanjan Banerjee

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