Redox exfoliated NbS2: characterization, stability, and oxidation.

Niobium disulfide is a layered transition metal dichalcogenide that is being exploited as a two-dimensional material. Although it is a superconductor at low temperatures and demonstrates great potential to be applied as a catalyst or co-catalyst in hydrogen evolution reactions, only a few reports have demonstrated the synthesis of a few-layer NbS2. However, before applications can be pursued, it is essential to understand the main characteristics of the obtained material and its stability under an atmospheric environment. In this work, we conducted a thorough characterization of redox-exfoliated NbS2 nanoflakes regarding their structure and stability in an oxygen-rich environment. Structural, morphological, and spectroscopic characterization demonstrated different fingerprints associated with distinct oxidation processes. This led us to identify oxide species and analyse the stability of the redox exfoliated NbS2 nanosheets in air, suggesting the most likely reaction pathways during the NbS2 interaction with oxygen, which agrees with our density-functional theory results. The mastery over the stability of layered materials is of paramount importance to target future applications, mainly because the electronic properties of these materials are strongly affected by an oxidizing environment.

A Critical Analysis on the Sensitivity Enhancement of Surface Plasmon Resonance Sensors with Graphene.

The use of graphene in surface plasmon resonance sensors, covering a metallic (plasmonic) film, has a number of demonstrated advantages, such as protecting the film against corrosion/oxidation and facilitating the introduction of functional groups for selective sensing. Recently, a number of works have claimed that few-layer graphene can also increase the sensitivity of the sensor. However, graphene was treated as an isotropic thin film, with an out-of-plane refractive index that is identical to the in-plane index. Here, we critically examine the role of single and few layers of graphene in the sensitivity enhancement of surface plasmon resonance sensors. Graphene is introduced over the metallic film via three different descriptions: as an atomic-thick two-dimensional sheet, as a thin effective isotropic material (same conductivity in the three coordinate directions), and as an non-isotropic layer (different conductivity in the perpendicular direction to the two-dimensional plane). We find that only the isotropic layer model, which is known to be incorrect for the optical modeling of graphene, provides sizable sensitivity increases, while the other, more accurate, models lead to a negligible contribution to the sensitivity.

3d transition metal coordination on monolayer MoS2: a facile doping method to functionalize surfaces.

Two-dimensional materials (2DM) have attracted much interest due to their distinct optical, electronic, and catalytic properties. These properties can be tuned by a range of methods including substitutional doping and, as recently demonstrated, by surface functionalization with single atoms, thus increasing the 2DM portfolio. We theoretically and experimentally describe the coordination reaction between MoS2 monolayers and 3d transition metals (TMs), exploring their nature and MoS2-TM interactions. Density functional theory calculations, X-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) spectroscopy point to the formation of MoS2-TM coordination complexes, where the adsorption energy for 3d TMs resembles the crystal-field (CF) stabilization energy for weak-field complexes. Pearson's theory for hard-soft acid-base and ligand-field theory were used to discuss the periodic trends of 3d TM coordination on MoS2 monolayer surfaces. We found that softer acids with higher ligand field stabilization energy, such as Ni2+, tend to form bonds with more covalent character with MoS2, which can be considered a soft base. On the other hand, harder acids, such as Cr3+, tend to form more ionic bonds. Additionally, we studied the trends in charge transfer and doping observed from XPS and PL results, where metals like Ni led to n-type doping. In contrast, Cu functionalization results in p-type doping. Therefore, the formation of coordination complexes on TMD's surface is a potentially effective way to control and understand the nature of single-atom functionalization of TMD monolayers without relying on or creating new defects.

Second-harmonic generation enhancement in monolayer transition-metal dichalcogenides by using an epsilon-near-zero substrate.

Monolayer transition-metal dichalcogenides (TMDCs) present high second-order optical nonlinearity, which is extremely desirable for, e.g., frequency conversion in nonlinear photonic devices. On the other hand, the atomic thickness of 2D materials naturally leads to low frequency converted intensities, highlighting the importance of designing structures that enhance the nonlinear response for practical applications. A number of methods to increase the pump electric field at 2D materials have been reported, relying on complex plasmonic and/or metasurface structures. Here, we take advantage of the fact that unstructured substrates with a low refractive index naturally maximize the pump field at a dielectric interface, offering a simple means to promote enhanced nonlinear optical effects. In particular, we measured second harmonic generation (SHG) in MoS2 and WS2 on fluorine tin oxide (FTO), which presents an epsilon-near zero point near our 1550 nm pump wavelength. Polarized SHG measurements reveal an SHG intensity that is one order of magnitude higher on FTO than on a glass substrate.

Spontaneous chemical functionalization via coordination of Au single atoms on monolayer MoS2.

Surface functionalization of metallic and semiconducting 2D transition metal dichalcogenides (TMDs) have mostly relied on physi- and chemi-sorption at defect sites, which can diminish the potential applications of the decorated 2D materials, as structural defects can have substantial drawbacks on the electronic and optoelectronic characteristics. Here, we demonstrate a spontaneous defect-free functionalization method consisting of attaching Au single atoms to monolayers of semiconducting MoS2(1H) via S-Au-Cl coordination complexes. This strategy offers an effective and controllable approach for tuning the Fermi level and excitation spectra of MoS2 via p-type doping and enhancing the thermal boundary conductance of monolayer MoS2, thus promoting heat dissipation. The coordination-based method offers an effective and damage-free route of functionalizing TMDs and can be applied to other metals and used in single-atom catalysis, quantum information devices, optoelectronics, and enhanced sensing.

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.

Real-time optofluidic surface-enhanced Raman spectroscopy based on a graphene oxide/gold nanorod nanocomposite.

We demonstrate a glass microcapillary fiber as an optofluidic platform for surface enhanced Raman spectroscopy (SERS), the inner walls of which are coated with a graphene oxide (GO)/gold nanorod (AuNR) nanocomposite. A simple thermal method is used for the coating, allowing for the continuous deposition of the nanocomposite without surface functionalization. We show that the AuNRs can be directly and nondestructively identified on the GO inside the capillaries via identification of the Au-Br SERS peak, as Br- ions from the AuNR synthesis remain on their surface. The coated microcapillary platform is, then, used as a stable SERS substrate for the detection of Rhodamine 6G (R6G) and Rhodamine 640 (RH640) at concentrations down to 10-7 and 10-9 M, respectively. As the required sample volumes are as low as a few hundred nanoliters, down to ~75 femtograms of analyte can be detected. The fiber also allows for the detection of the molecules at acquisition times as low as 0.05 s, indicating the platform's suitability for real-time sensing.

Resonantly Increased Optical Frequency Conversion in Atomically Thin Black Phosphorus.

Optical frequency conversion via the nonlinear effect of third harmonic generation is shown to be resonantly enhanced in few-layer black phosphorus. This feature is believed to be a consequence of exciton-related resonance, as the enhancement is strongly correlated with the observation of exciton-recombination photoluminescence. Few-layer thicknesses are obtained both via mechanical exfoliation and laser thinning.

Graphene Based Waveguide Polarizers: In-Depth Physical Analysis and Relevant Parameters.

Optical polarizing devices exploiting graphene embedded in waveguides have been demonstrated in the literature recently and both the TE- and TM-pass behaviors were reported. The determination of the passing polarization is usually attributed to graphene's Fermi level (and, therefore, doping level), with, however, no direct confirmation of this assumption provided. Here we show, through numerical simulation, that rather than graphene's Fermi level, the passing polarization is determined by waveguide parameters, such as the superstrate refractive index and the waveguide's height. The results provide a consistent explanation for experimental results reported in the literature. In addition, we show that with an accurate graphene modeling, a waveguide cannot be switched between TE pass and TM pass via Fermi level tuning. Therefore, the usually overlooked contribution of the waveguide design is shown to be essential for the development of optimized TE- or TM-pass polarizers, which we show to be due to the control it provides on the fraction of the electric field that is tangential to graphene.

Unusual angular dependence of the Raman response in black phosphorus.

Anisotropic materials are characterized by a unique optical response, which is highly polarization-dependent. Of particular interest are layered materials formed by the stacking of two-dimensional (2D) crystals that are naturally anisotropic in the direction perpendicular to the 2D planes. Black phosphorus (BP) is a stack of 2D phosphorene crystals and a highly anisotropic semiconductor with a direct band gap. We show that the angular dependence of polarized Raman spectra of BP is rather unusual and can be explained only by considering complex values for the Raman tensor elements. This result can be traced back to the electron-photon and electron-phonon interactions in this material.

Fabrication and optical characterization of silica optical fibers containing gold nanoparticles.

Gold nanoparticles have been used since antiquity for the production of red-colored glasses. More recently, it was determined that this color is caused by plasmon resonance, which additionally increases the material's nonlinear optical response, allowing for the improvement of numerous optical devices. Interest in silica fibers containing gold nanoparticles has increased recently, aiming at the integration of nonlinear devices with conventional optical fibers. However, fabrication is challenging due to the high temperatures required for silica processing and fibers with gold nanoparticles were solely demonstrated using sol-gel techniques. We show a new fabrication technique based on standard preform/fiber fabrication methods, where nanoparticles are nucleated by heat in a furnace or by laser exposure with unprecedented control over particle size, concentration, and distribution. Plasmon absorption peaks exceeding 800 dB m(-1) at 514-536 nm wavelengths were observed, indicating higher achievable nanoparticle concentrations than previously reported. The measured resonant nonlinear refractive index, (6.75 ± 0.55) × 10(-15) m(2) W(-1), represents an improvement of >50×.

Integrated polarizers based on tapered highly birefringent photonic crystal fibers.

This paper proposes and demonstrates the creation of sections with a high polarization dependent loss (PDL) in a commercial highly birefringent (polarization maintaining) photonic crystal fiber (PCF), via tapering with pressure applied to the holes. The tapers had a 1-cm-long uniform section with a 66% scale reduction, in which the original microstructure aspect ratio was kept by the pressure application. The resulting waveguides show polarizing action across the entire tested wavelength range, 1510-1600 nm, with a peak PDL of 35.3 dB/cm (c.f. ~1 dB/cm for a typical commercial polarizing fiber). The resulting structure, as well as its production, is extremely simple, and enable a small section with a high PDL to be obtained in a polarization maintaining PCF, meaning that the polarization axes in the polarizing and polarization maintaining sections are automatically aligned.

Temperature response of an all-solid photonic bandgap fiber for sensing applications.

The spectral shift due to temperature in the photonic bandgap (PBG) of an all-solid PBG fiber is investigated, aiming at discrete and distributed temperature sensing. A temperature rise induces a red shift in the bandgap spectra, which can be easily and precisely monitored by measuring the fiber transmission near one of the band edges. Two different situations that are potentially compatible with distributed and quasi-distributed sensing were investigated: heating a 2 m section of a longer (~10 m) fiber, and heating the whole extension of a fiber that is tens of centimeters in length and was spliced to conventional fibers on both sides. The latter setup yielded bandgap spectral shifts up to ~35 pm/°C. Aiming at discrete sensing, a short (~50 mm) fiber section was subjected to a tight bend so as to exhibit increased temperature sensitivity. Choosing the position of the bend allows for reconfiguration, on demand, of the sensor. A semi-analytical method to identify the spectral position of bandgaps was used to model the fiber transmission, as well as the bandgap shift with temperature, with consistent results.

Quasi-phase-matched second harmonic generation in silicon nitride ring resonators controlled by static electric field.

Actively-controlled second harmonic generation in a silicon nitride ring resonator is proposed and simulated. The ring was designed to resonate at both pump and second harmonic wavelengths and quasi-phase-matched frequency conversion is induced by a periodic static electric field generated by voltage applied to electrodes arranged along the ring. Nonlinear propagation simulations were undertaken and an efficiency of -21.67 dB was calculated for 60 mW of pump power at 1550 nm and for a 30V applied voltage, which compares favorably with demonstrated all-optical second harmonic generation in integrated microresonators. Transient effects were also evaluated. The proposed design can be exploited for the construction of electro-optical devices based on nonlinear effects in CMOS compatible circuits.

Selectively coupling core pairs in multicore photonic crystal fibers: optical couplers, filters and polarization splitters for space-division-multiplexed transmission systems.

Selective coupling a single pair of cores in a photonic crystal fiber with multiple, initially decoupled, cores is demonstrated through the use of a technique to locally post-process the fiber cross section. Coupling occurs when the hole between the selected core pair is collapsed over a short fiber section, which is accomplished by heating the section while the hole is submitted to an air pressure that is lower than that applied to all other holes in the microstructure. The demonstrated couplers present an estimated insertion loss of ~1 dB and exhibit spectral modulations with a depth of up to 18 dB and a high polarization sensitivity that can be exploited for polarization splitting or filtering in space-division-multiplexed optical interconnection and telecommunication links.

Efficient and short-range light coupling to index-matched liquid-filled hole in a solid-core photonic crystal fiber.

A photonic crystal fiber (PCF) with a section of one of the holes next to the solid core filled with an index-matched liquid is studied. Liquid filling alters the core geometry, which locally comprises the original silica core, the liquid channel and the silica around it. It is demonstrated that when light reaches the filled section, it periodically and efficiently couples to the liquid, via the excitation of a number of modes of the composite core, with coupling lengths ranging from tens to hundreds of microns. The resulting modal-interference-modulated spectrum shows temperature sensitivity as high as 5.35 nm/°C. The proposed waveguide geometry presents itself as an interesting way to pump and/or to probe liquid media within the fiber, combining advantages usually found separately in liquid-filled hollow-core PCFs (high light-liquid overlap) and in solid-core PCFs (low insertion losses). Therefore, pumping and luminescence guiding with a PCF filled with a Rhodamine solution is also demonstrated.

In-fiber modal Mach-Zehnder interferometer based on the locally post-processed core of a photonic crystal fiber.

We demonstrate a novel, compact and low-loss photonic crystal fiber modal Mach-Zehnder interferometer with potential applications to sensing and WDM telecommunications. By selectively collapsing a ~1-mm-long section of a hole next to the solid core, a pair of modes of the post-processed structure are excited and interfere at its exit. A modulation depth of up to ~13 dB and an insertion loss as low as 2.8 dB were achieved. A temperature sensitivity of -53.4 pm/°C was measured, making the device suitable for temperature sensing.

All-fiber devices based on photonic crystal fibers with integrated electrodes.

A special kind of microstructured optical fiber is proposed and fabricated in which, in addition to the holey region (solid core and silica-air cladding), two large holes exist for electrode insertion. Either Bi-Sn or Au- Sn alloys were selectively inserted into the large holes forming two parallel, continuous and homogeneous internal electrodes. We demonstrate the production of a monolithic device and its use to externally control some of the guidance properties (e.g. polarization) of the fiber.

Random fiber laser.

We investigate the effects of two-dimensional confinement on the lasing properties of a classical random laser system operating in the incoherent feedback (diffusive) regime. A suspension of 250 nm rutile (TiO2) particles in a rhodamine 6G solution was inserted into the hollow core of a photonic crystal fiber generating the first random fiber laser and a novel quasi-one-dimensional random laser geometry. A comparison with similar systems in bulk format shows that the random fiber laser presents an efficiency that is at least 2 orders of magnitude higher.