Sub-10 nm Nanoparticle Detection Using Multi-Technique-Based Micro-Raman Spectroscopy.

Microplastic pollution is a growing public concern as these particles are ubiquitous in various environments and can fragment into smaller nanoplastics. Another environmental concern arises from widely used engineered nanoparticles. Despite the increasing abundance of these nano-sized pollutants and the possibility of interactions with organisms at the sub cellular level, with many risks still being unknown, there are only a few publications on this topic due to the lack of reliable techniques for nanoparticle characterization. We propose a multi-technique approach for the characterization of nanoparticles down to the 10 nm level using standard micro-Raman spectroscopy combined with standard atomic force microscopy. We successfully obtained single-particle spectra from 25 nm sized polystyrene and 9 nm sized TiO2 nanoparticles with corresponding mass limits of detection of 8.6 ag (attogram) and 1.6 ag, respectively, thus demonstrating the possibility of achieving an unambiguous Raman signal from a single, small nanoparticle with a resolution comparable to more complex and time-consuming technologies such as Tip-Enhanced Raman Spectroscopy and Photo-Induced Force Microscopy.

Tunable Visible Light and Energy Transfer Mechanism in Tm3+ and Silver Nanoclusters within Co-Doped GeO2-PbO Glasses.

This study introduces a novel method for producing Ag nanoclusters (NCs) within GeO2-PbO glasses doped with Tm3+ ions. Sample preparation involved the melt-quenching method, employing adequate heat treatment to facilitate Ag NC formation. Absorption spectroscopy confirmed trivalent rare-earth ion incorporation. Ag NC identification and the amorphous structure were observed using transmission electron microscopy. A tunable visible emission from blue to the yellow region was observed. The energy transfer mechanism from Ag NCs to Tm3+ ions was demonstrated by enhanced 800 nm emission under 380 and 400 nm excitations, mainly for samples with a higher concentration of Ag NCs; moreover, the long lifetime decrease of Ag NCs at 600 nm (excited at 380 and 400 nm) and the lifetime increase of Tm3+ ions at 800 nm (excitation of 405 nm) corroborated the energy transfer between those species. Therefore, we attribute this energy transfer mechanism to the decay processes from S1→T1 and T1→S0 levels of Ag NCs to the 3H4 level of Tm3+ ions serving as the primary path of energy transfer in this system. GeO2-PbO glasses demonstrated potential as materials to host Ag NCs with applications for photonics as solar cell coatings, wideband light sources, and continuous-wave tunable lasers in the visible spectrum, among others.

1337 nm Emission of a Nd3+-Doped TZA Glass Random Laser.

Random lasers have been studied using many materials, but only a couple have used glass matrices. Here, we present a study of zinc tellurite and aluminum oxide doped with different percentages of neodymium oxide (4 wt.%, 8 wt.%, and 16 wt.%) and demonstrate for the first time random laser action at 1337 nm. Laser emission was verified and the laser pulse's rise time and input-output power slope were obtained. A cavity composed of the sample's pump surface and an effective mirror formed by a second, parallel layer at the gain-loss boundary was probably the main lasing mechanism of this random laser system. The reason for the absence of emission at 1064 nm is thought to be a measured temperature rise in the samples' active volume.

Silver Nanoclusters Tunable Visible Emission and Energy Transfer to Yb3+ Ions in Co-Doped GeO2-PbO Glasses for Photonic Applications.

This work investigates the optical properties of Yb3+ ions doped GeO2-PbO glasses containing Ag nanoclusters (NCs), produced by the melt-quenching technique. The lack in the literature regarding the energy transfer (ET) between these species in these glasses motivated the present work. Tunable visible emission occurs from blue to orange depending on the Yb3+ concentration which affects the size of the Ag NCs, as observed by transmission electron microscopy. The ET mechanism from Ag NCs to Yb3+ ions (2F7/2 → 2F5/2) was attributed to the S1→T1 decay (spin-forbidden electronic transition between singlet-triplet states) and was corroborated by fast and slow lifetime decrease (at 550 nm) of Ag NCs and photoluminescence (PL) growth at 980 nm, for excitations at 355 and 405 nm. The sample with the highest Yb3+ concentration exhibits the highest PL growth under 355 nm excitation, whereas at 410 nm it is the sample with the lowest concentration. The restriction of Yb3+ ions to the growth of NCs is responsible for these effects. Thus, higher Yb3+ concentration forms smaller Ag NCs, whose excitation at 355 nm leads to more efficient ET to Yb3+ ions compared to 410 nm. These findings have potential applications in the visible to near-infrared regions, such as tunable CW laser sources and photovoltaic devices.

Effect of Silver Nanoparticles on the Optical Properties of Double Line Waveguides Written by fs Laser in Nd3+-Doped GeO2-PbO Glasses.

Nd3+-doped GeO2-PbO glass with silver (Ag) nanoparticles (NPs) are produced with double line waveguides through fs laser processing for photonic applications. A Ti:sapphire fs laser at 800 nm was used to write the waveguides directly into the glass 0.7 mm beneath the surface. This platform is based on pairs of parallel lines with spacing of 10 µm, each pair being formed by two identical written lines but in two different configurations of 4 or 8 separately processed lines, which are coincident. The results of optical microscopy, absorbance measurements, refractive index change, beam quality factor (at 632 and 1064 nm), photoluminescence, propagation losses, and relative gain at 1064 nm are presented. The structural changes in the glass due to the presence of Ag NPs were investigated by Raman spectroscopy. At 632 and 1064 nm, x,y-symmetrical guiding was observed, and for both kinds of overlapping pulses, a refractive index alteration of 10-3 was found in both directions. Photoluminescence growth of ~47% at 1064 nm was observed due to the plasmonic effect of Ag NPs. In dual waveguides containing Ag NPs, the relative gain obtained increased by 40% and 30% for four and eight overlapping lines, respectively, at 600 mW of 808 nm pump power, when compared to waveguides without those metallic NPs. We highlight the resultant positive internal gains of 5.11 and 7.12 dB/cm that showed a growth of ~40% and ~30%, respectively, with respect to the samples without Ag NPs. The increase in photoluminescence and relative gain were related to the local field growth produced by Ag NPs. The present results show that the addition of Ag NPs impacts positively on the optical performance at 1064 nm of double line waveguides processed by fs laser writing in Nd3+-doped GeO2-PbO glass, opening news perspectives for photonics.

Probing the Strong Near-IR Two-Photon Transition in Supramolecular Triphenylamine-based Polymers by Nonlinear Absorption Spectroscopy.

Due to their capability of film formation and remarkable optical features, semiconductor polymers with high two-photon absorption (2PA) have been studied as potential candidates for the development of organic photonic platforms. Furthermore, there is a high demand for photonic devices operating in the near-infrared (IR) region. However, the magnitude of the nonlinear optical response of random coil polymers in the IR region is weak due to the loss of molecular structure caused by increasing the π-conjugated backbone. Thus, herein we aim to investigate the molecular structure and 2PA features relationship for four polymers with supramolecular (helical) rodlike structure. Such polymers have a rigid core based on triphenylamine groups connected to the chiral binaphthalene units and a strong electron-withdrawing group (EWG). This kind of structure allows a very high chromophore density, which was responsible for generating 2PA cross-section between 305 GM and 565 GM in the near-IR (900-1300 nm), depending on the EWG strength. in light of the two-level model within the sum-overstates approach, we estimated the degree of intramolecular charge transfer induced by 2PA in the IR region, and values as high as 50-70% were found. Such a critical outcome allows the 2PA cross-section in the IR region to remain high even though the ratio between the visible/IR-band 2PA cross-section increases as a function of EWG strength.

Two-photon absorption properties of BODIPY-like compounds based on BF2-naphthyridine complexes.

Boron dipyrromethene type molecules (BODIPYs) are versatile molecules which have been used for applications ranging from photodynamic therapy to solar cells (DSSC). However, these molecules usually do not present high two-photon absorption cross-sections, limiting their use in nonlinear optical applications. Herein, we study a series of BF2-naphthyridine based boron-complexes with electron-donating and withdrawing groups to increase their two-photon absorption. We have found two-photon absorption cross-sections up to approximately 270 GM, which corresponds to an increase of approximately five times in comparison to the average cross-section value reported for molecules with similar conjugation length, indicating such compounds as potential materials for nonlinear applications in both the visible and infrared spectral regions.