Second-Order Nonlinearity of Graphene Quantum Dots Measured by Hyper-Rayleigh Scattering.

The first hyperpolarizability of graphene quantum dots (GQDs) suspended in water was determined using the hyper-Rayleigh scattering (HRS) technique. To the best of our knowledge, this is the first application of the HRS technique to characterize GQDs. Two commercial GQDs (Acqua-Cyan and Acqua-Green) with different compositions were studied. The HRS experiments were performed with an excitation laser at 1064 nm. The measured hyperpolarizabilities were (1.0±0.1)×10-27 esu and (0.9±0.1)×10-27 esu for Acqua-Cyan and Acqua-Green, respectively. The results were used to estimate the hyperpolarizability per nanosheet obtained by assuming that each GQD has five nanosheets with 0.3 nm thickness. The two-level model, used to calculate the static hyperpolarizability per nanosheet, provides values of (2.4±0.1)×10-28 esu (Acqua-Cyan) and (0.5±0.1)×10-28 esu (Aqua-Green). The origin of the nonlinearity is discussed on the basis of polarized resolved HRS experiments, and electric quadrupolar behavior with a strong dependence on surface effects. The nontoxic characteristics and order of magnitude indicate that these GQDs may be useful for biological microscopy imaging.

Intensity-Dependent Optical Response of 2D LTMDs Suspensions: From Thermal to Electronic Nonlinearities.

The nonlinear optical (NLO) response of photonic materials plays an important role in the understanding of light-matter interaction as well as pointing out a diversity of photonic and optoelectronic applications. Among the recently studied materials, 2D-LTMDs (bi-dimensional layered transition metal dichalcogenides) have appeared as a beyond-graphene nanomaterial with semiconducting and metallic optical properties. In this article, we review most of our work in studies of the NLO response of a series of 2D-LTMDs nanomaterials in suspension, using six different NLO techniques, namely hyper Rayleigh scattering, Z-scan, photoacoustic Z-scan, optical Kerr gate, and spatial self-phase modulation, besides the Fourier transform nonlinear optics technique, to infer the nonlinear optical response of semiconducting MoS2, MoSe2, MoTe2, WS2, semimetallic WTe2, ZrTe2, and metallic NbS2 and NbSe2. The nonlinear optical response from a thermal to non-thermal origin was studied, and the nonlinear refraction index and nonlinear absorption coefficient, where present, were measured. Theoretical support was given to explain the origin of the nonlinear responses, which is very dependent on the spectro-temporal regime of the optical source employed in the studies.

Random lasing and replica symmetry breaking in GeO2-PbO-MgO glass-ceramics doped with neodymium.

We investigated the random lasing process and Replica Symmetry Breaking (RSB) phenomenon in neodymium ions (Nd3+) doped lead-germanate glass-ceramics (GCs) containing MgO. Glass samples were fabricated by conventional melt-quenching technique and the GCs were obtained by carefully devitrifying the parent glasses at 830 °C for different time intervals. The partial crystallization of the parent glasses was verified by X-ray diffraction. Photoluminescence (PL) enhancement of [Formula: see text] 500% relative to the parent glasses was observed for samples with a higher crystallinity degree (annealed during 5 h). Powders with grains having average size of 2 µm were prepared by griding the GCs samples. The Random Laser (RL) was excited at 808 nm, in resonance with the Nd3+ transition 4I9/2 → {4F5/2, 2H9/2}, and emitted at 1068 nm (transition 4F3/2 → 4I11/2). The RL performance was clearly enhanced for the sample with the highest crystallinity degree whose energy fluence excitation threshold (EFEth) was 0.25 mJ/mm2. The enhanced performance is attributed to the residence-time growth of photons inside the sample and the higher quantum efficiency of Nd3+ incorporated within the microcrystals, where radiative losses are reduced. Moreover, the phenomenon of Replica Symmetry Breaking (RSB), characteristic of a photonic-phase-transition, was detected by measuring the intensity fluctuations of the RL emission. The Parisi overlap parameter was determined for all samples, for excitation below and above the EFEth. This is the first time, for the best of the authors knowledge, that RL emission and RSB are reported for a glass-ceramic system.

Simultaneous evaluation of intermittency effects, replica symmetry breaking and modes dynamics correlations in a Nd:YAG random laser.

Random lasers (RLs) are remarkable experimental platforms to advance the understanding of complex systems phenomena, such as the replica-symmetry-breaking (RSB) spin glass phase, dynamics modes correlations, and turbulence. Here we study these three phenomena jointly in a Nd:YAG based RL synthesized for the first time using a spray pyrolysis method. We propose a couple of modified Pearson correlation coefficients that are simultaneously sensitive to the emergence and fading out of photonic intermittency turbulent-like effects, dynamics evolution of modes correlations, and onset of RSB behavior. Our results show how intertwined these phenomena are in RLs, and suggest that they might share some common underlying mechanisms, possibly approached in future theoretical models under a unified treatment.

Fifth-order optical nonlinear response of semiconducting 2D LTMD MoS2.

The effective fifth-order susceptibility, ${\chi}_{\rm eff}^{(5)}$, of two-dimensional (2D) semiconducting layered transition metal dichalcogenide (LTMD) molybdenum disulfide (${\rm MoS}_2$) is reported here for the first time, to the best of our knowledge. Using the $ Z $-scan technique with a laser operating at 800 nm, 1 kHz, 100 fs, we investigated the nonlinear behavior of ${\rm MoS}_2$ suspended in acetonitrile (concentration, 70 µg/ml). The effective nonlinear refractive index ${{n}_{4,{eff}}} = - ({7.6 \pm 0.5}) \times {10^{- 26}}\; {{\rm cm}^4}/{{\rm W}^2}$, proportional to ${\rm Re}{\chi}_{\rm eff}^{(5)}$, was measured for monolayer ${\rm MoS}_2$ nanoflakes, prepared by a modified redox exfoliation method. We also determined the value of the nonlinear refractive index ${{n}_2} = + ({4.8 \pm 0.5}) \times {10^{- 16}}\;{{\rm cm}^2}/{\rm W}$, which is related to the material's effective third-order optical susceptibility real part, ${Re\chi}_{\rm eff}^{(3)}$. For comparison, we also investigated the nonlinear response of tungsten disulfide (${\rm WS}_2$) monolayers, prepared by the same method and suspended in acetonitrile (concentration, 40 µg/ml), which only exhibited the third-order nonlinear effect in the same intensity range, up to ${120}\;{{{\rm GW}/{\rm cm}}^2}$. Nonlinear absorption was not observed in either ${\rm MoS}_2$ or ${\rm WS}_2$.

Hyper-Rayleigh scattering in 2D redox exfoliated semi-metallic ZrTe2 transition metal dichalcogenide.

Nonlinear optical characterization of nanostructured layered transition metal dichalcogenides (LTMDs) is of fundamental interest for basic knowledge and applied purposes. In particular, second-order optical nonlinearities are the basis for second harmonic generation as well as sum or difference frequency generation and have been studied in some 2D TMDs, especially in those with a semiconducting character. Here we report, for the first time, on the second-order nonlinearity of the semi-metallic ZrTe2 monolayer in acetonitrile suspension (concentration of 4.9 × 1010 particles per cm3), synthesized via a modified redox exfoliation method and characterized using the Hyper-Rayleigh scattering technique in the nanosecond regime. The orientation-averaged first-hyperpolarizability was found to be ß(2ω) = (7.0 ± 0.3) × 10-24 esu per ZrTe2 monolayer flake, the largest reported so far. Polarization-resolved measurements were performed in the monolayer suspension and indicate the dipolar origin of the generated incoherent second harmonic wave.

Monolayer 2D ZrTe2 transition metal dichalcogenide as nanoscatter for random laser action.

We demonstrate random laser emission from Rhodamine 6G with ZrTe2 transition metal dichalcogenide (TMD) as nanoscatters, both in powder and 2D nanoflakes liquid suspension. The 2D semimetal ZrTe2 was synthesized by a modified redox exfoliation method to provide single layer TMD, which was employed for the first time as the scatter medium to provide feedback in an organic gain medium random laser. In order to exploit random laser emission and its threshold value, replica symmetry breaking leading to a photonic paramagnetic to photonic spin glass transition in both 2D and 3D (powder) ZrTe2 was demonstrated. One important aspect of mixing organic dyes with ZrTe2 is that there is no chemical reaction leading to dye degradation, demonstrated by operating over more than 2 hours of pulsed (5 Hz) random laser emission.

UV random laser emission from flexible ZnO-Ag-enriched electrospun cellulose acetate fiber matrix.

We report an alternative random laser (RL) architecture based on a flexible and ZnO-enriched cellulose acetate (CA) fiber matrix prepared by electrospinning. The electrospun fibers, mechanically reinforced by polyethylene oxide and impregnated with zinc oxide powder, were applied as an adsorbent surface to incorporate plasmonic centers (silver nanoprisms). The resulting structures - prepared in the absence (CA-ZnO) and in the presence of silver nanoparticles (CA-ZnO-Ag) - were developed to support light excitation, guiding and scattering prototypes of a RL. Both materials were excited by a pulsed (5 Hz, 5 ns) source at 355 nm and their fluorescence emission monitored at 387 nm. The results suggest that the addition of silver nanoprisms to the ZnO- enriched fiber matrix allows large improvement of the RL performance due to the plasmon resonance of the silver nanoprisms, with ~80% reduction in threshold energy. Besides the intensity and spectral analysis, the RL characterization included its spectral and intensity angular dependences. Bending the flexible RL did not affect the spectral characteristics of the device. No degradation was observed in the random laser emission for more than 10,000 shots of the pump laser.

Phosphotellurite glass and glass-ceramics with high TeO2 contents: thermal, structural and optical properties.

Phosphotellurite based glasses have interesting features such as low characteristic temperatures, high glass forming ability, high thermal stability against crystallization and a broad transparency window from ultraviolet (UV) to near-infrared (NIR), which makes them promising materials for photonic applications. In this work, phosphotellurite binary glasses, having a composition (100 - x)TeO2 - xBa(PO3)2 with x varying from 1 to 20 mol%, were synthesized by the conventional melt-quenching method in covered gold crucibles under air. Optical, physical and structural properties of the new glass samples were investigated by differential scanning calorimetry, X-ray diffraction, Raman spectroscopy, transmission electron microscopy, linear optical absorption from UV to NIR, IR transmittance, and optical limiting experiments. Transparent glass-ceramics in the visible range were obtained for phosphotellurite samples containing 2, 4 and 6 mol% of Ba(PO3)2 and the phase crystallization was investigated through Rietveld analysis and transmission electron microscopy. The incorporation of Ba(PO3)2 into the TeO2 network drastically increases the thermal stability against devitrification and helps to shift the infrared multiphonon absorption edge to longer wavelengths. Nonlinear measurements performed with a picosecond laser at 532 nm indicate large effective nonlinear absorption coefficients for all samples. In summary, the dependence of the spectroscopic properties on the compositions of the samples revealed promising transparent glass and glass-ceramics for photonic applications.