Stability and SERS signal strength of laser-generated gold, silver, and bimetallic nanoparticles at different KCl concentrations.

Noble metal nanoparticles, specifically gold and silver, are extensively utilized in sensors, catalysts, surface-enhanced Raman scattering (SERS), and optical-electronic components due to their unique localized surface plasmon resonance (LSPR) properties. The production of these nanoparticles involves various methods, but among the environmentally friendly approaches, laser ablation stands out as it eliminates the need for toxic chemicals during purification. However, nanoparticle aggregation poses a challenge in laser ablation, necessitating the addition of extra materials that contaminate the otherwise clean process. In this study, we investigate the effectiveness of a biocompatible material, potassium chloride (KCl), in preventing particle aggregation. Although salt is known to trigger aggregation, we observed that certain concentrations of KCl can slow down this process. Over an eight-week period, we examined the aggregation rate, extinction behavior, and stability of gold, silver, and hybrid nanoparticles generated in different KCl concentrations. Extinction spectra, SEM images, SERS signal strength, and zeta potential were analyzed. Our results demonstrate that laser ablation in water and salt solutions yields nanoparticles with a spherical shape and a negative zeta potential. Importantly, we identified the optimal concentration of potassium chloride salt that maintains solution stability and SERS signal strength. Adsorbed chloride ions on silver nanoparticles were evidenced by low-frequency SERS band near 242 cm-1. A better understanding of the effect of KCl concentration on the properties of noble metal nanoparticles can lead to improved generation protocols and the development of tailored nanoparticle systems with enhanced stability and SERS activity.

Multiwavelength SERS of Magneto-Plasmonic Nanoparticles Obtained by Combined Laser Ablation and Solvothermal Methods.

The present study introduces a novel method for the synthesis of magneto-plasmonic nanoparticles (MPNPs) with enhanced functionality for surface-enhanced Raman scattering (SERS) applications. By employing pulsed laser ablation in liquid (PLAL) to synthesize plasmonic nanoparticles and wet chemistry to synthesize magnetic nanoparticles, we successfully fabricated chemically pure hybrid Fe3O4@Au and Fe3O4@Ag nanoparticles. We demonstrated a straightforward approach of an electrostatic attachment of the plasmonic and magnetic parts using positively charged polyethylenimine. The MPNPs displayed high SERS sensitivity and reproducibility, and the magnetic part allowed for the controlled separation of the nanoparticles from the reaction mixture, their subsequent concentration, and their precise deposition onto a specified surface area. Additionally, we fabricated alloy based MPNPs from AgxAu100-x (x = 50 and 80 wt %) targets with distinct localized surface plasmon resonance (LSPR) wavelengths. The compositions, morphologies, and optical properties of the nanoparticles were characterized by using transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), UV-vis spectroscopy, and multiwavelength Raman spectroscopy. A standard SERS marker, 4-mercaptobenzoic acid (4-MBA), validated the enhancement properties of the MPNPs and found an enhancement factor of 2 × 108 for the Fe3O4@Ag nanoparticles at 633 nm excitation. Lastly, we applied MPNP-enhanced Raman spectroscopy for the analysis of the biologically relevant molecule adenine and found a limit of detection of 10-7 M at 785 nm excitation. The integration of PLAL and wet chemical methods enabled the relatively fast and cost-effective production of MPNPs characterized by high SERS sensitivity and signal reproducibility that are required in various fields, including biomedicine, food safety, materials science, security, and defense.

High Spectral Sensitivity of Strongly Coupled Hybrid Tamm-Plasmonic Resonances for Biosensing Application.

In this study, the sensitivity to the refractive index changes of the ambient was studied on the uniform gold film (~50 nm) with a 1D photonic crystal (PC) from periodic five TiO2 (~110 nm)/SiO2 (~200 nm) bilayers and gold nano-bumps array produced by direct laser writing on the same sample. The optical signal sensitivity of hybrid plasmonic resonances was compared with traditional surface plasmon resonance (SPR) on a single gold layer. The influence of the strong coupling regime between Tamm plasmon polariton (TPP) and propagated plasmon polaritons in the hybrid plasmonic modes on the sensitivity of the optical was discussed. Recent studies have shown very high hybrid plasmonic mode sensitivity SHSPP ≈ 26,000 nm/RIU to the refractive index on the uniform gold layer; meanwhile, the introduction of gold lattice reduces the signal sensitivity, but increases the Q-factor of the plasmonic resonances. Despite this, the sensitivity to the ellipsometric parameters Ψ and Δ on the gold lattice was rather high due to the increased Q-factor of the resonances. The comparison of plasmonic resonance sensitivity to the refractive index changes of hybrid TPP-SPP mode on the uniform gold layer and traditional SPR have shown that hybrid plasmonic mode, due to a strong coupling effect, overcomes the SPR by about 27%.

Gold Nanoparticles Generated Using the Nanosecond Laser Treatment of Multilayer Films and Their Use for SERS Applications.

Surface-enhanced Raman spectroscopy (SERS) substrates fabricated using a repeated laser treatment of thin gold films are demonstrated. The presented SERS substrates consist of the gold nanoparticles, whose density and size depend on the used film thickness and number of treated films. The larger number of the treated gold film layers increases the amount of larger nanoparticles (size >20 nm). However, a large number of small nanoparticles (5-20 nm) in all cases is also observed. The manufactured SERS substrates exhibit a high enhancement factor, which is in the range of 106. The enhancement factor can be increased by adding an additional Au coating on the top of nanoparticles generated from a single gold layer. The demonstrated laser-based fabrication approach of large-scale SERS substrates is simple, reliable, without the use of chemicals for the reduction and stabilization of nanoparticles, and cost-effective.

Thermal control of SZ2080 photopolymerization in four-beam interference lithography.

Photopolymerization by four-beam interference lithography on a preheated SZ2080 sample was explored at different initial temperatures of the sample: 20 °C, 50 °C, 75 °C, 100 °C, 125 °C, and 150 °C, and at exposure times ranging from 0.5 s to 5 s. The average laser power selected was ∼100 mW for the 300 ps duration pulses at a 1 kHz repetition rate. The experimental results demonstrate that the higher initial temperature of the sample positively influences the crosslinking of the patterns. These findings will improve polymerization protocols for multi-beam interference lithography.

Laser Irradiation of Gd-Si and Gd-Si-Ge Colloid Mixtures for the Fabrication of Compound Nanoparticles.

Binary (Gd5 Si4 , GdSi) and ternary (Gd5 Si2 Ge2 ) compound nanoparticles (NPs) were prepared by laser irradiation of a mixture of colloidal solutions containing NPs of the relevant elements. It is assumed that the compound NPs are formed by heating, co-melting, and chemical interactions in the alloyed droplets. The blackbody-like radiation of the heated NPs was used for temperature control of the NP-preparation process. The obtained results demonstrate that laser irradiation of colloidal NPs provides unique possibilities not only for the synthesis of compound NPs but also for control of their phase composition and size. The synthesized Gd-based compound NPs exhibited magnetic transition at an ordering temperature, TC , in the range of 310-320 K. Thus, the magnetic properties of the synthesized particles confirm their potential for biomedical applications, in particular, for magnetic hyperthermia treatment.

Nanoscale thermal diffusion during the laser interference ablation using femto-, pico-, and nanosecond pulses in silicon.

Laser interference ablation in silicon using femto-, pico-, and nanosecond pulses was investigated. The experimental and computational results provide information about nanoscale thermal diffusion during the ultra-short laser-matter interaction. The temperature modulation depth was introduced as a parameter for quality assessment of laser interference ablation. Based on the experiments and calculations, a new semi-empirical formula which combines the interference period with the laser pulse duration, the thermal modulation depth and the thermal diffusivity of the material was derived. This equation is in excellent agreement with the experimental and modelling results of laser interference ablation. This new formula can be used for selecting the appropriate pulse duration for periodical structuring with the required resolution and quality.

Photo-polymerization differences by using nanosecond and picosecond laser pulses.

Formation of polymeric pillars by using laser interference lithography is compared for nanosecond and picosecond laser pulses. The experimental results are explained by dynamics of laser-excited radicals. The shape of fabricated structures demonstrates that thermal accumulation and oxygen diffusion from the surrounding air make an influence on polymerization when the pulse duration is in the nanosecond range. By using picosecond laser pulses, the thermal accumulation and oxygen diffusion effects are not important for low repetition rate (500 Hz), and they become relevant only at the repetition rates higher than ≥ 1 kHz. It is shown that thermal accumulation is caused by a low-temperature diffusivity and heat accumulation at the polymer-glass interface, and it plays a significant role in the final shape of the structures fabricated using the nanosecond laser pulses.

Bessel-like beam array formation by periodical arrangement of the polymeric round-tip microstructures.

Here, we report the formation of Bessel-like beam array from periodic patterns fabricated by the four-beam interference lithography. Characteristics of the generated Bessel-like beams depend on geometrical parameters of the fabricated microaxicon-like structures, which can be easily controlled via the laser processing parameters. The output beam characteristics disclose the attributes of Bessel beams. The demonstrated method enables an easy fabrication of angular-tolerant wavefront detectors, optical tweezers, optical imaging systems or materials processing tools, having a broad range of applications.

3D alkyne-azide cycloaddition: spatiotemporally controlled by combination of aryl azide photochemistry and two-photon grafting.

A novel fluoroaryl azide with an alkyne tail was synthesized and precisely immobilized within a PEG-based matrix via two-photon induced decomposition and nitrene insertion. Well defined 3D positioning of the terminal alkyne allows site-specific micropatterning. The subsequent 3D alkyne-azide cycloaddition was realized using dye-functionalized molecules containing "clickable" azide moieties.