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.

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 ${\rm WS}_2$.

Nonlinear photoacoustic response of suspensions of laser-synthesized plasmonic titanium nitride nanoparticles.

A nonlinear photoacoustic (PA) response from solutions of 40 nm plasmonic titanium nitride nanoparticles (NPs) synthesized by laser ablation in a liquid environment (acetone) is reported. Using a photoacoustic Z-scan with 5 ns pumping pulses, values of effective nonlinear absorption (NLA) coefficients ßPA,eff were measured and found to be 3.27±0.17 × 10-8, 6.41±0.32 × 10-8, and 3.22±0.16 × 10-8 for 600, 700, and 800 nm pumping wavelengths, respectively. To take into account the influence of nonlinear scattering, absorption-dependent PA measurements were carried out together with the optical Z-scan, and the obtained data were compared. The origin of the effective absorptive nonlinearity is discussed based on combined NLA in NPs, nonlinear scattering, and bubble generation triggered by NP-mediated light absorption. Potential applications include biomedical diagnostics and therapy.

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.

Nonlinear refractive index of electric field aligned gold nanorods suspended in index matching oil measured with a Hartmann-Shack wavefront aberrometer.

The capability to dynamically control the nonlinear refractive index of plasmonic suspensions may enable innovative nonlinear sensing and signaling nanotechnologies. Here, we experimentally determine the effective nonlinear refractive index for gold nanorods suspended in an index matching oil aligned using electric fields, demonstrating an approach to modulate the nonlinear optical properties of the suspension. The nonlinear optical experiments were carried out using a Hartmann-Shack wavefront aberrometer in a collimated beam configuration with a high repetition rate femtosecond laser. The suspensions were probed at 800 nm, overlapping with the long-axis absorption peak of the nanorods. We find that the effective nonlinear refractive index of the gold nanorods suspension depends linearly on the orientational order parameter, S, which can be understood by a thermally induced nonlinear response. We also show the magnitude of the nonlinear response can be varied by ∼ 60%.

Linear and nonlinear optical characterization of self-assembled, large-area gold nanosphere metasurfaces with sub-nanometer gaps: errata.

We correct a nomenclature error for the plasmon ruler equation used to fit the simulation data in Fig. 2(d) [Opt. Express24, 27360 (2016)].

Linear and nonlinear optical characterization of self-assembled, large-area gold nanosphere metasurfaces with sub-nanometer gaps.

We created centimeter-scale area metasurfaces consisting of a quasi-hexagonally close packed monolayer of gold nanospheres capped with alkanethiol ligands on glass substrates using a directed self-assembly approach. We experimentally characterized the morphology and the linear and nonlinear optical properties of metasurfaces. We show these metasurfaces, with interparticle gaps of 0.6 nm, are modeled well using a classical (without charge transfer) description. We find a large dispersion of linear refractive index, ranging from values less than vacuum, 0.87 at 600 nm, to Germanium-like values of 4.1 at 880 nm, determined using spectroscopic ellipsometry. Nonlinear optical characterization was carried out using femtosecond Z-scan and we observe saturation behavior of the nonlinear absorption (NLA) and nonlinear refraction (NLR). We find a negative NLR from these metasurfaces two orders of magnitude larger (n2,sat = -7.94x10-9 cm2/W at Isat,n2 = 0.43 GW/cm2) than previous reports on gold nanostructures at similar femtosecond time scales. We also find the magnitude of the NLA comparable to the largest values reported (ß2,sat = -0.90x105 cm/GW at Isat,ß2 = 0.34 GW/cm2). Precise knowledge of the index of refraction is of crucial importance for emerging dispersion engineering technologies. Furthermore, utilizing this directed self-assembly approach enables the nanometer scale resolution required to develop the unique optical response and simultaneously provides high-throughput for potential device realization.