Can Koral

Nanoparticle-Enhanced Laser-Induced Breakdown Spectroscopy of Metallic Samples

In this article, an increase of 1-2 orders of magnitude in laser-induced breakdown spectroscopy (LIBS) signals was obtained by depositing silver nanoparticles on metal samples. Nanoparticle-enhanced LIBS (NELIBS) was found to be a robust and flexible tool for the chemical analysis of metals because the sample emission signal did not appear to be affected much by the size and concentration of deposited nanoparticles (NPs) within the ranges of 10 nm for diameter and 1 order of magnitude for concentration. On the other hand, preliminary NELIBS tests on insulators and semiconductors did not show any significant enhancement with respect to conventional LIBS. In this article, we present a detailed investigation of the fundamental features of NELIBS spectra, in addition to some examples of analytical applications to the quantitative analysis of metal alloys.

Nanoparticle Enhanced Laser-Induced Breakdown Spectroscopy for Microdrop Analysis at subppm Level

In this paper, nanoparticle enhanced laser-induced breakdown spectroscopy (NELIBS) was applied to the elemental chemical analysis of microdrops of solutions with analyte concentration at subppm level. The effect on laser ablation of the strong local enhancement of the electromagnetic field allows enhancing the optical emission signal up to more than 1 order of magnitude, enabling LIBS to quantify ppb concentration and notably decreasing the limit of detection (LOD) of the technique. At optimized conditions, it was demonstrated that NELIBS can reach an absolute LOD of few picograms for Pb and 0.2 pg for Ag. The effect of field enhancement in NELIBS was tested on biological solutions such as protein solutions and human serum, in order to improve the sensitivity of LIBS with samples where the formation and excitation of the plasma are not as efficient as with metals. Even in these difficult cases, a significant improvement with respect to conventional LIBS was observed.

Perspective on the use of nanoparticles to improve LIBS analytical performance: nanoparticle enhanced laser induced breakdown spectroscopy (NELIBS)

In this paper, the new approach for Laser Induced Breakdown Spectroscopy (LIBS) based on nanoparticle deposition on the sample surface is reviewed from both fundamental and application points of view. The case of Nanoparticle-Enhanced LIBS (NELIBS) of metal samples is used for describing and discussing the main causes of the emission signal enhancement. A set of test cases is presented, which shows enhancements up to 1–2 orders of magnitude obtained using NELIBS with respect to LIBS. The feasibility and potential of NELIBS are also discussed for several analytical applications, including analysis of metallic samples, transparent samples and aqueous solutions.

Nanoparticle-Enhanced Laser Induced Breakdown Spectroscopy for the noninvasive analysis of transparent samples and gemstones

In this paper, Nanoparticle-Enhanced Laser Induced Breakdown Spectroscopy is applied to transparent samples and gemstones with the aim to overcome the laser induced damage on the sample. We propose to deposit a layer of AuNPs on the sample surface by drying a colloidal solution before ablating the sample with a 532 nm pulsed laser beam. This procedure ensures that the most significant fraction of the beam, being in resonance with the AuNP surface plasmon, is mainly absorbed by the NP layer, which in turn results the breakdown to be induced on NPs rather than on the sample itself. The fast explosion of the NPs and the plasma induction allow the ablation and the transfer in the plasma phase of the portion of sample surface where the NPs were placed. The employed AuNPs are prepared in milliQ water without the use of any chemical stabilizers by Pulsed Laser Ablation in Liquids (PLAL), in order to obtain a strict control of composition and impurities, and to limit possible spectral interferences (except from Au emission lines). Therefore with this technique it is possible to obtain, together with the emission signal of Au (coming from atomized NPs), the emission spectrum of the sample, by limiting or avoiding the direct interaction of the laser pulse with the sample itself. This approach is extremely useful for the elemental analysis by laser ablation of high refractive index samples, where the laser pulse on an untreated surface can otherwise penetrate inside the sample, generate breakdown events below the superficial layer, and consequently cause cracks and other damage. The results obtained with NELIBS on high refractive index samples like glasses, tourmaline, aquamarine and ruby are very promising, and demonstrate the potentiality of this approach for precious gemstones analysis.

Fundamental Study and Analytical Applications of Nanoparticle-Enhanced Laser-Induced Breakdown Spectroscopy (NELIBS) of Metals, Semiconductors and Insulators

Nanoparticle-Enhanced Laser-Induced Breakdown Spectroscopy (NELIBS) is a recently proposed method to efficiently increase the LIBS emission signal of metals up to 2 orders of magnitude, by depositing metal nanoparticles (NPs) on the sample surface (De Giacomo A, Gaudiuso R, Koral C, Dell’Aglio M, De Pascale O Anal Chem 85). This considerable emission enhancement has been ascribed to two effects: (1) an improvement in the ablation effect, and (2) a more efficient production of seed electrons by field emission, in turn due to the enhancement of the laser electromagnetic field induced by the NPs themselves (De Giacomo A, Gaudiuso R, Koral C, Dell’Aglio M, De Pascale O Acta Part B, 98).

Terahertz Time-Domain Study of Silver Nanoparticles Synthesized by Laser Ablation in Organic Liquid

We report the investigation of laser-synthesized Ag nanoparticles (Ag-NPs) in an organic liquid environment by using terahertz time-domain spectroscopy (THz-TDS) technique. Colloidal Ag-NPs with an average diameter of 10 nm in two-propanol solution through nanosecond pulsed laser ablation were synthesized. THz-TDS measurements were performed on different volumetric concentration of Ag-NPs suspensions placed in 2-mm path length quartz cuvette. Due to the dispersive and highly absorptive nature of the nano liquids, an approach based on extracting the optical properties through the changes in amplitude and phase solely around the main peak of THz waveform is developed. This approach allowed for an accurate estimation of the complex refractive index of the Metallic-NPs suspension for the different prepared volumetric concentrations. In addition, using Maxwell-Garnett theory, the NP concentration is also extracted. This method shows that the time-domain nature of the THz pulse measurement technique is extremely useful in instances where slight variations in highly dispersive samples need to be investigated.