Manipulation of nonlinear optical responses in layered ferroelectric niobium oxide dihalides.

Realization of highly tunable second-order nonlinear optical responses, e.g., second-harmonic generation and bulk photovoltaic effect, is critical for developing modern optical and optoelectronic devices. Recently, the van der Waals niobium oxide dihalides are discovered to exhibit unusually large second-harmonic generation. However, the physical origin and possible tunability of nonlinear optical responses in these materials remain to be unclear. In this article, we reveal that the large second-harmonic generation in NbOX2 (X = Cl, Br, and I) may be partially contributed by the large band nesting effect in different Brillouin zone. Interestingly, the NbOCl2 can exhibit dramatically different strain-dependent bulk photovoltaic effect under different polarized light, originating from the light-polarization-dependent orbital transitions. Importantly, we achieve a reversible ferroelectric-to-antiferroelectric phase transition in NbOCl2 and a reversible ferroelectric-to-paraelectric phase transition in NbOI2 under a certain region of external pressure, accompanied by the greatly tunable nonlinear optical responses but with different microscopic mechanisms. Our study establishes the interesting external-field tunability of NbOX2 for nonlinear optical device applications.

Ultrathin quantum light source with van der Waals NbOCl2 crystal.

Interlayer electronic coupling in two-dimensional materials enables tunable and emergent properties by stacking engineering. However, it also results in significant evolution of electronic structures and attenuation of excitonic effects in two-dimensional semiconductors as exemplified by quickly degrading excitonic photoluminescence and optical nonlinearities in transition metal dichalcogenides when monolayers are stacked into van der Waals structures. Here we report a van der Waals crystal, niobium oxide dichloride (NbOCl2), featuring vanishing interlayer electronic coupling and monolayer-like excitonic behaviour in the bulk form, along with a scalable second-harmonic generation intensity of up to three orders higher than that in monolayer WS2. Notably, the strong second-order nonlinearity enables correlated parametric photon pair generation, through a spontaneous parametric down-conversion (SPDC) process, in flakes as thin as about 46 nm. To our knowledge, this is the first SPDC source unambiguously demonstrated in two-dimensional layered materials, and the thinnest SPDC source ever reported. Our work opens an avenue towards developing van der Waals material-based ultracompact on-chip SPDC sources as well as high-performance photon modulators in both classical and quantum optical technologies1-4.

Highly Efficient 2D NIR-II Photothermal Agent with Fenton Catalytic Activity for Cancer Synergistic Photothermal-Chemodynamic Therapy.

Photothermal therapy (PTT) has emerged as a promising cancer therapeutic modality with high therapeutic specificity, however, its therapeutic effectiveness is limited by available high-efficiency photothermal agents (PTAs), especially in the second near-infrared (NIR-II) biowindow. Here, based on facile liquid-exfoliated FePS3 nanosheets, a highly efficient NIR-II PTA with its photothermal conversion efficiency of up to 43.3% is demonstrated, which is among the highest reported levels in typical PTAs. More importantly, such Fe-based 2D nanosheets also show superior Fenton catalytic activity facilitated by their ultrahigh specific surface area, simultaneously enabling cancer chemodynamic therapy (CDT). Impressively, the efficiency of CDT could be further remarkably enhanced by its photothermal effect, leading to cancer synergistic PTT/CDT. Both in vitro and in vivo studies reveal a highly efficient tumor ablation under NIR-II light irradiation. This work provides a paradigm for cancer CDT and PTT in the NIR-II biowindow via a single 2D nanoplatform with desired therapeutic effect. Furthermore, with additional possibilities for magnetic resonance imaging, photoacoustic tomography, as well as drug loading, this Fe-based 2D material could potentially serve as a 2D "all-in-one" theranostic nanoplatform.

Broadly Tunable Plasmons in Doped Oxide Nanoparticles for Ultrafast and Broadband Mid-Infrared All-Optical Switching.

Plasmons in conducting nanostructures offer the means to efficiently manipulate light at the nanoscale with subpicosecond speed in an all-optical operation fashion, thus allowing for construction of high performance all-optical signal-processing devices. Here, by exploiting the ultrafast nonlinear optical properties of broadly tunable mid-infrared (MIR) plasmons in solution-processed, degenerately doped oxide nanoparticles, we demonstrate ultrafast all-optical switching in the MIR region, which features subpicosecond response speed (with recovery time constant of <400 fs) as well as an ultrabroadband response spectral range (covering 3.0-5.0 µm). Furthermore, with the degenerately doped nanoparticles as Q-switch, pulsed fiber lasers covering 2.0-3.5 µm were constructed, of which a watt-level fiber laser at 3.0 µm band shows superior overall performance among previously reported passively Q-switched fiber lasers at the same band. Notably, the degenerately doped nanoparticles show great potential to work in the spectral range over 3.0 µm, which is beyond the accessibility of commercially available but expensive semiconducting saturable absorber mirror (SESAM). Our work demonstrates a versatile while cost-effective material solution to ultrafast photonics in the technologically important MIR region.

A Solution-Processed Ultrafast Optical Switch Based on a Nanostructured Epsilon-Near-Zero Medium.

All the optical properties of materials are derived from dielectric function. In spectral region where the dielectric permittivity approaches zero, known as epsilon-near-zero (ENZ) region, the propagating light within the material attains a very high phase velocity, and meanwhile the material exhibits strong optical nonlinearity. The interplay between the linear and nonlinear optical response in these materials thus offers unprecedented pathways for all-optical control and device design. Here the authors demonstrate ultrafast all-optical modulation based on a typical ENZ material of indium tin oxide (ITO) nanocrystals (NCs), accessed by a wet-chemistry route. In the ENZ region, the authors find that the optical response in these ITO NCs is associated with a strong nonlinear character, exhibiting sub-picosecond response time (corresponding to frequencies over 2 THz) and modulation depth up to ≈160%. This large optical nonlinearity benefits from the highly confined geometry in addition to the ENZ enhancement effect of the ITO NCs. Based on these ENZ NCs, the authors successfully demonstrate a fiber optical switch that allows switching of continuous laser wave into femtosecond laser pulses. Combined with facile processibility and tunable optical properties, these solution-processed ENZ NCs may offer a scalable and printable material solution for dynamic photonic and optoelectronic devices.

Emerging Low-Dimensional Materials for Nonlinear Optics and Ultrafast Photonics.

Low-dimensional (LD) materials demonstrate intriguing optical properties, which lead to applications in diverse fields, such as photonics, biomedicine and energy. Due to modulation of electronic structure by the reduced structural dimensionality, LD versions of metal, semiconductor and topological insulators (TIs) at the same time bear distinct nonlinear optical (NLO) properties as compared with their bulk counterparts. Their interaction with short pulse laser excitation exhibits a strong nonlinear character manifested by NLO absorption, giving rise to optical limiting or saturated absorption associated with excited state absorption and Pauli blocking in different materials. In particular, the saturable absorption of these emerging LD materials including two-dimensional semiconductors as well as colloidal TI nanoparticles has recently been utilized for Q-switching and mode-locking ultra-short pulse generation across the visible, near infrared and middle infrared wavelength regions. Beside the large operation bandwidth, these ultrafast photonics applications are especially benefit from the high recovery rate as well as the facile processibility of these LD materials. The prominent NLO response of these LD materials have also provided new avenues for the development of novel NLO and photonics devices for all-optical control as well as optical circuits beyond ultrafast lasers.

Cu-Sn-S plasmonic semiconductor nanocrystals for ultrafast photonics.

Here, we show that solution-processed Cu-Sn-S semiconductor nanocrystals (NCs) demonstrate a tunable localized surface plasmon resonance band in the near infrared region, where strong saturable absorption occurs. A saturable absorber based on these plasmonic NCs enables the construction of a stable mode-locked femtosecond fiber laser operating at the telecommunication band.

Universal Near-Infrared and Mid-Infrared Optical Modulation for Ultrafast Pulse Generation Enabled by Colloidal Plasmonic Semiconductor Nanocrystals.

Field effect relies on the nonlinear current-voltage relation in semiconductors; analogously, materials that respond nonlinearly to an optical field can be utilized for optical modulation. For instance, nonlinear optical (NLO) materials bearing a saturable absorption (SA) feature an on-off switching behavior at the critical pumping power, thus enabling ultrafast laser pulse generation with high peak power. SA has been observed in diverse materials preferably in its nanoscale form, including both gaped semiconductor nanostructures and gapless materials like graphene; while the presence of optical bandgap and small carrier density have limited the active spectral range and intensity. We show here that solution-processed plasmonic semiconductor nanocrystals exhibit superbroadband (over 400 THz) SA, meanwhile with large modulation depth (∼7 dB) and ultrafast recovery (∼315 fs). Optical modulators fabricated using these plasmonic nanocrystals enable mode-locking and Q-switching operation across the near-infrared and mid-infrared spectral region, as exemplified here by the pulsed lasers realized at 1.0, 1.5, and 2.8 µm bands with minimal pulse duration down to a few hundreds of femtoseconds. The facile accessibility and superbroadband optical nonlinearity offered by these nonconventional plasmonic nanocrystals may stimulate a growing interest in the exploiting of relevant NLO and photonic applications.

Ultra-broadband nonlinear saturable absorption of high-yield MoS2 nanosheets.

High-yield MoS2 nanosheets with strong nonlinear optical (NLO) responses in a broad near-infrared range were synthesized by a facile hydrothermal method. The observation of saturable absorption, which was excited by the light with photon energy smaller than the gap energy of MoS2, can be attributed to the enhancement of the hybridization between the Mo d-orbital and S p-orbital by the oxygen incorporation into MoS2. High-yield MoS2 nanosheets with high modulation depth and large saturable intensity generated a stable, passively Q-switched fiber laser pulse at 1.56 µm. The high output power of 1.08 mW can be attained under a very low pump power of 30.87 mW. Compared to recently reported passively Q-switched fiber lasers utilizing exfoliated MoS2 nanosheets, the efficiency of the laser for our passive Q-switching operation is larger and reaches 3.50%. This research may extend the understanding on the NLO properties of MoS2 and indicate the feasibility of the high-yield MoS2 nanosheets to passively Q-switched fiber laser effectively at low pump strengths.

Topological engineering of glass for modulating chemical state of dopants.

A novel approach to modulating the chemical state of dopants by engineering the topological features of a glass matrix is presented. The method allows selective stabilization of dopants on a wide range of length scales, from dispersed ions to aggregated clusters to nanoparticles, leading to various intriguing optical phenomena, such as great emission enhancement and ultra-broadband optical amplification.

Origin of structural relaxation dependent spectroscopic features of bismuth-activated glasses.

For the first time, we studied the effect of structural relaxation on the NIR spectroscopic properties of bismuth-activated germanium glasses below glass transition temperature. Interestingly, distinct change behavior of NIR luminescence is observed at two different heat-treatment temperature ranges corresponding to two different relaxation behavior of glass structure. Besides, when structural modified by partly substituting B(2)O(3) for GeO(2), a narrower and more thermal sensitive luminescence is observed, which is inexplicable by "inhomogeneous broadening" and we tentatively attribute it to a defect-involved reason. Fundamentally the results here not only provide us a deeper insight into the optical property of bismuth-activated materials but also increase our understanding of the glassy state, and practically it delivers some valuable guidance in designing bismuth-activated glasses with superior NIR optical properties.

Enhanced broadband excited upconversion luminescence in Ho-doped glasses by codoping with bismuth.

We report enhanced green and red upconversion (UC) luminescence in Ho3+-doped oxyfluoride germanate glass by introducing bismuth near-infrared active centers as sensitizers. The UC excitation bands at 750 and 970 nm show a full width at half-maximum of 20 and 45 nm, respectively. Energy transfer from sensitizers, the excited-state absorption, and phonon-coupled absorption of Ho3+ jointly contribute to the enhanced UC luminescence. Our approach provides an efficient methodology to broaden the excitation bandwidth of UC luminescent materials, which may have the potential for promising application in solar cells.

Lanthanide-doped NaGdF4 core-shell nanoparticles for non-contact self-referencing temperature sensors.

We report that non-contact self-referencing temperature sensors can be realized with the use of core-shell nanostructures. These lanthanide-based nanothermometers (NaGdF4:Yb(3+)/Tm(3+)@Tb(3+)/Eu(3+)) exhibit higher sensitivity in a wide range from 125 to 300 K based on two emissions of Tb(3+) at 545 nm and Eu(3+) at 615 nm under near-infrared laser excitation.

Regulation of structure rigidity for improvement of the thermal stability of near-infrared luminescence in Bi-doped borate glasses.

The effect of heat-treatment on the near-infrared (NIR) luminescence properties was studied in Bi-doped borate glasses. The luminescence intensity generally decreases with the increase of temperature, and the thermal stability can be improved by nearly 4.5 times with addition of 5 mol% La2O3. Collaborative studies by using steady photoluminescence (PL) and photoluminescence excitation (PLE) spectra, luminescence decay curve, differential thermal analysis (DTA), Raman spectra and X-ray diffraction (XRD) indicate that the luminescence decrement is associated with the agglomeration of Bi active centers during heat-treatment. The improvement of the thermal stability of NIR luminescence with the addition of La2O3 is benefited from the enhancement of structure rigidity due to the strong cationic field strength of La3+. The results not only provide valuable guidance for suppressing performance degradation of Bi-doped glass during fiber drawing process, but also present an effective way to control the luminescence properties of main group elements in glasses from the perspective of glass structure.