Ultrafast nonequilibrium dynamic process of separate electrons and holes during exciton formation in few-layer tungsten disulfide.

Femtosecond transient absorption spectroscopy has been employed to unravel separate initial nonequilibrium dynamic processes of photo-injected electrons and holes during the formation process of the lowest excitons at the K-valley in few-layer tungsten disulfide. Charge carrier thermalization and cooling, as well as concomitant many-body effects on the exciton resonances, are distinguished. The thermalization of holes is observed to be faster than that of electrons. Both of them proceed predominantly via carrier-carrier scattering, as evidenced by the observed dependence of the thermalization time on pump fluences. The fluence dependent time constants also suggest that the subsequent cooling for electrons is probably dominated by acoustic phonons, whereas for holes it is mostly controlled by LO phonons. An extremely fast red- and blue-shift crossover followed by a slow blue-shift of exciton resonance was observed in the temporal evolution of exciton resonances by resonant exciton A excitation. The rapid red-shift could be due to the strong screening of the Coulomb interaction between quasi-free charge carriers in electron-hole plasma. The subsequent slow blue-shift is the net result of the competition among many-body effects in the hot-exciton cooling process. Our findings elucidate the carrier-selective ultrafast dynamics and their many-body effects, underpinning new possibilities for developing optoelectronic devices based on transport properties of a single type of carrier.

Coherent phonon dynamics in a c-plane sapphire crystal before and after intense femtosecond laser irradiation.

Femtosecond pump-probe experiments with a ∼6.4 fs time-resolution were performed to investigate the coherent phonon dynamics in a c-plane sapphire crystal before and after intense 800 nm femtosecond laser irradiation. The intense femtosecond laser induced defect/distortion and even re-crystallization of crystalline structures, which result in the appearance of new peaks and relative intensity change in coherent phonon and Raman spectra. The combination of these two spectra was found to be beneficial to evidence the variation of crystalline structure and further to differentiate the origins of new Raman peaks after irradiation. Further analysis of time-dependent differential absorbance with damped cosine function fitting and Fourier transfer calculation yields the vibrational parameters, including periods, damping times and initial phases, before and after irradiation. With these parameters, the defect-effects on damping time and the mechanism of coherent phonon generation were addressed.

Enhancement of nonlinear functionality of step-index silica fibers combining thermal poling and 2D materials deposition.

This work proposes a new route to overcome the limits of the thermal poling technique for the creation of second order nonlinearity in conventional silica optical fibers. We prove that it is possible to enhance the nonlinear behavior of periodically poled fibers merging the effects of poling with the nonlinear intrinsic properties of some materials, such as MoS2, which are deposited inside the cladding holes of a twin-hole silica fiber. The optical waves involved in a second harmonic generation process partially overlap inside the thin film of the nonlinear material and exploit its higher third order susceptibility to produce an enhanced SHG.

Composite material anti-resonant optical fiber electromodulator with a 3.5 dB depth.

The hollow regions of an anti-resonant fiber (ARF) offer an excellent template for the deposition of functional materials. When the optical properties of such materials can be modified via external stimuli, it offers a method to control the transmission properties of the fiber device. In this Letter, we show that the integration of a ${{\rm MoS}_2}$MoS2 film into the ARF voids allows the fiber to act as an electro-optical modulator. We record a maximum modulation depth of 3.5 dB at 744 nm, with an average insertion loss of 7.5 dB.

Probing Excitons, Trions, and Dark Excitons in Monolayer WS2 Using Resonance Raman Spectroscopy.

We present temperature-dependent resonance Raman measurements on monolayer WS2 for the temperature range 4-295 K using excitation photon energies from 1.9 to 2.15 eV in ∼7 meV steps. These are analyzed to determine the resonance profiles of five previously assigned phonon based Raman peaks (A1', E', 2ZA, LA, 2LA) and a previously unassigned peak at 485 cm-1 whose possible attributions are discussed. The resonance profiles obtained are fitted to a perturbation theory derived model and it is shown that both excitons and trions are required to explain the profiles. The model is used to separate the contribution of exciton-exciton, trion-trion, and exciton-trion scattering to each of the Raman peaks at 4 K. This separation allows the ratios of the rates of scattering involving the A1' and E' phonons for each of the three types of scattering to be determined. The explanation of the multiphonon Raman peaks requires the coupling of bright excitons and trions to large wavevector dark states. The fitting of the resonance Raman profiles for these Raman peaks demonstrates scattering of bright excitons to bright trions via these large wavevector dark states.

Optical-resonance-enhanced nonlinearities in a MoS2-coated single-mode fiber.

Few-layer molybdenum disulfide (MoS2) has an electronic band structure that is dependent on the number of layers and, therefore, is a very promising material for an array of optoelectronic, photonic, and lasing applications. In this Letter, we make use of a side-polished optical fiber platform to gain access to the nonlinear optical properties of the MoS2 material. We show that the nonlinear response can be significantly enhanced via resonant coupling to the thin film material, allowing for the observation of optical modulation and spectral broadening in the telecom band. This route to access the nonlinear properties of two-dimensional materials promises to yield new insights into their photonic properties.

Spin-orbit splitting in single-layer MoS2 revealed by triply resonant Raman scattering.

Although new spintronic devices based on the giant spin-orbit splitting of single-layer MoS(2) have been proposed, such splitting has not been studied effectively in experiments. This Letter reports the valence band spin-orbit splitting in single-layer MoS(2) for the first time, probed by the triply resonant Raman scattering process. We found that upon 325 nm laser irradiation, the second order overtone and combination Raman modes of single-layer MoS(2) are dramatically enhanced. Such resonant Raman enhancement arises from the electron-two-phonon triple resonance via the deformation potential and Fröhlich interaction. As a sensitive and precise probe for the spin-orbit splitting, the triply resonant Raman scattering will provide a new and independent route to study the spin characteristics of MoS(2).

Conformal CVD-Grown MoS2 on Three-Dimensional Woodpile Photonic Crystals for Photonic Bandgap Engineering.

To achieve the modification of photonic band structures and realize the dispersion control toward functional photonic devices, composites of photonic crystal templates with high-refractive-index material are fabricated. A two-step process is used: 3D polymeric woodpile templates are fabricated by a direct laser writing method followed by chemical vapor deposition of MoS2. We observed red-shifts of partial bandgaps at the near-infrared region when the thickness of deposited MoS2 films increases. A ∼10 nm red-shift of fundamental and high-order bandgap is measured after each 1 nm MoS2 thin film deposition and confirmed by simulations and optical measurements using an angle-resolved Fourier imaging spectroscopy system.

Laser-induced crystalline optical waveguide in glass fiber format.

We report on the first fabrication of a glass fiber based laser-induced crystalline waveguide. The glass and crystal are based on the stoichiometric composition of (La,Yb)BGeO(5). A laser induced waveguide has been fabricated on the surface of a ribbon glass fiber using milliwatt-level continuous wave UV laser radiation at a fast scanning speed. Evidence of crystallinity in the created structure was observed using micro-Raman spectroscopy and scanning electron microscopy. Preliminary investigations on the waveguiding behavior and the nonlinear performance in the crystalline waveguide are reported.

Low Energy Switching of Phase Change Materials Using a 2D Thermal Boundary Layer.

The switchable optical and electrical properties of phase change materials (PCMs) are finding new applications beyond data storage in reconfigurable photonic devices. However, high power heat pulses are needed to melt-quench the material from crystalline to amorphous. This is especially true in silicon photonics, where the high thermal conductivity of the waveguide material makes heating the PCM energy inefficient. Here, we improve the energy efficiency of the laser-induced phase transitions by inserting a layer of two-dimensional (2D) material, either MoS2 or WS2, between the silica or silicon substrate and the PCM. The 2D material reduces the required laser power by at least 40% during the amorphization (RESET) process, depending on the substrate. Thermal simulations confirm that both MoS2 and WS2 2D layers act as a thermal barrier, which efficiently confines energy within the PCM layer. Remarkably, the thermal insulation effect of the 2D layer is equivalent to a ∼100 nm layer of SiO2. The high thermal boundary resistance induced by the van der Waals (vdW)-bonded layers limits the thermal diffusion through the layer interface. Hence, 2D materials with stable vdW interfaces can be used to improve the thermal efficiency of PCM-tuned Si photonic devices. Furthermore, our waveguide simulations show that the 2D layer does not affect the propagating mode in the Si waveguide; thus, this simple additional thin film produces a substantial energy efficiency improvement without degrading the optical performance of the waveguide. Our findings pave the way for energy-efficient laser-induced structural phase transitions in PCM-based reconfigurable photonic devices.

Facilitating Uniform Large-Scale MoS2, WS2 Monolayers, and Their Heterostructures through van der Waals Epitaxy.

The fabrication process for the uniform large-scale MoS2, WS2 transition-metal dichalcogenides (TMDCs) monolayers, and their heterostructures has been developed by van der Waals epitaxy (VdWE) through the reaction of MoCl5 or WCl6 precursors and the reactive gas H2S to form MoS2 or WS2 monolayers, respectively. The heterostructures of MoS2/WS2 or WS2/MoS2 can be easily achieved by changing the precursor from WCl6 to MoCl5 once the WS2 monolayer has been fabricated or switching the precursor from MoCl5 to WCl6 after the MoS2 monolayer has been deposited on the substrate. These VdWE-grown MoS2, WS2 monolayers, and their heterostructures have been successfully deposited on Si wafers with 300 nm SiO2 coating (300 nm SiO2/Si), quartz glass, fused silica, and sapphire substrates using the protocol that we have developed. We have characterized these TMDCs materials with a range of tools/techniques including scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), micro-Raman analysis, photoluminescence (PL), atomic force microscopy (AFM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), and selected-area electron diffraction (SAED). The band alignment and large-scale uniformity of MoS2/WS2 heterostructures have also been evaluated with PL spectroscopy. This process and resulting large-scale MoS2, WS2 monolayers, and their heterostructures have demonstrated promising solutions for the applications in next-generation nanoelectronics, nanophotonics, and quantum technology.

Laser printed two-dimensional transition metal dichalcogenides.

Laser processing is a highly versatile technique for the post-synthesis treatment and modification of transition metal dichalcogenides (TMDCs). However, to date, TMDCs synthesis typically relies on large area CVD growth and lithographic post-processing for nanodevice fabrication, thus relying heavily on complex, capital intensive, vacuum-based processing environments and fabrication tools. This inflexibility necessarily restricts the development of facile, fast, very low-cost synthesis protocols. Here we show that direct, spatially selective synthesis of 2D-TMDCs devices that exhibit excellent electrical, Raman and photoluminescence properties can be realized using laser printing under ambient conditions with minimal lithographic or thermal overheads. Our simple, elegant process can be scaled via conventional laser printing approaches including spatial light modulation and digital light engines to enable mass production protocols such as roll-to-roll processing.

Smartphone Biosensor With App Meets FDA/ISO Standards for Clinical Pulse Oximetry and Can Be Reliably Used by a Wide Range of Patients.

BACKGROUND: Millions of smartphones contain a photoplethysmography (PPG) biosensor (Maxim Integrated) that accurately measures pulse oximetry. No clinical use of these embedded sensors is currently being made, despite the relevance of remote clinical pulse oximetry to the management of chronic cardiopulmonary disease, and the triage, initial management, and remote monitoring of people affected by respiratory viral pandemics, such as severe acute respiratory syndrome coronavirus 2 or influenza. To be used for clinical pulse oximetry the embedded PPG system must be paired with an application (app) and meet US Food and Drug Administration (FDA) and International Organization for Standardization (ISO) requirements. RESEARCH QUESTION: Does this smartphone sensor with app meet FDA/ISO requirements? Are measurements obtained using this system comparable to those of hospital reference devices, across a wide range of people? STUDY DESIGN AND METHODS: We performed laboratory testing addressing ISO and FDA requirements in 10 participants using the smartphone sensor with app. Subsequently, we performed an open-label clinical study on 320 participants with widely varying characteristics, to compare the accuracy and precision of readings obtained by patients with those of hospital reference devices, using rigorous statistical methodology. RESULTS: "Breathe down" testing in the laboratory showed that the total root-mean-square deviation of oxygen saturation (Spo2) measurement was 2.2%, meeting FDA/ISO standards. Clinical comparison of the smartphone sensor with app vs hospital reference devices determined that Spo2 and heart rate accuracy were 0.48% points (95% CI, 0.38-0.58; P < .001) and 0.73 bpm (95% CI, 0.33-1.14; P < .001), respectively; Spo2 and heart rate precision were 1.25 vs reference 0.95% points (P < .001) and 5.99 vs reference 3.80 bpm (P < .001), respectively. These small differences were similar to the variation found between two FDA-approved reference instruments for Spo2: accuracy, 0.52% points (95% CI, 0.41-0.64; P < .001) and precision, 1.01 vs 0.86% points (P < .001). INTERPRETATION: Our findings support the application for full FDA/ISO approval of the smartphone sensor with app tested for use in clinical pulse oximetry. Given the immense and immediate practical medical importance of remote intermittent clinical pulse oximetry to both chronic disease management and the global ability to respond to respiratory viral pandemics, the smartphone sensor with app should be prioritized and fast-tracked for FDA/ISO approval to allow clinical use. TRIAL REGISTRY: ClinicalTrials.gov; No.: NCT04233827; URL: www.clinicaltrials.gov.

Terahertz Analysis of CH3NH3PbI3 Perovskites Associated with Graphene and Silver Nanowire Electrodes.

In order to investigate the thermal and chemical (in)stabilities of MAPbI3 incorporated with graphene and silver nanowire (AgNW) electrodes, we employed the terahertz (THz) time-domain spectroscopy, which has a unique ability to deliver the information of electrical properties and the intermolecular bonding and crystalline nature of materials. In in situ THz spectroscopy of MAPbI3, we observed a slight blue-shift in frequency of the 2 THz phonon mode as temperatures increase across the tetragonal-cubic structural phase transition. For MAPbI3 with the graphene top electrode, no noticeable frequency shift is observed until the temperature reaches the maximum operating temperature of solar cells (85 °C). Phonon frequency shift is sensitive to the strain-induced tilt of PbI6 octahedra and our results indicate that graphene forms a stable interface with MAPbI3 and is also effective in suppression of the undesirable phase transition. Meanwhile, for MAPbI3 coupled with the AgNW bottom electrode, the THz conductivity was found to be as low as that of the MAPbI3 single layer, attributed to the chemical reaction between Ag atoms and iodide ions. The THz conductivity is greatly increased when an ultrathin Al2O3 interlayer is introduced to cover the AgNW network via the atomic layer deposition (ALD) method. ALD of Al2O3 on the AgNW surfaces at low temperature guarantees a conformal coating, which strongly affects the ohmic contacts between the NWs. Our results demonstrate the advantage of THz spectroscopy for the comprehensive analysis of thermal and chemical stabilities of perovskites associated with the electrode materials.

Solution-Based Synthesis of Few-Layer WS2 Large Area Continuous Films for Electronic Applications.

Unlike MoS2 ultra-thin films, where solution-based single source precursor synthesis for electronic applications has been widely studied, growing uniform and large area few-layer WS2 films using this approach has been more challenging. Here, we report a method for growth of few-layer WS2 that results in continuous and uniform films over centimetre scale. The method is based on the thermolysis of spin coated ammonium tetrathiotungstate ((NH4)2WS4) films by two-step high temperature annealing without additional sulphurization. This facile and scalable growth method solves previously encountered film uniformity issues. Atomic force microscopy (AFM) and transmission electron microscopy (TEM) were used to confirm the few-layer nature of WS2 films. Raman and X-Ray photoelectron spectroscopy (XPS) revealed that the synthesized few-layer WS2 films are highly crystalline and stoichiometric. Finally, WS2 films as-deposited on SiO2/Si substrates were used to fabricate a backgated Field Effect Transistor (FET) device for the first time using this precursor to demonstrate the electronic functionality of the material and further validate the method.

Triboelectrification of Two-Dimensional Chemical Vapor Deposited WS2 at Nanoscale.

Triboelectric properties of chemical vapor deposited WS2 nanoflakes have been characterized in nano-range by atomic force microscopy (AFM) and Kelvin force microscopy (KFM). The triboelectric process is dependent on the thickness of WS2 nanoflakes, and it is sensitive to the adsorbates like water molecules, as well as transferred Pt from the tip on the sample. The density of tribo-charge can be modified by applying various biases to the conductive Pt-coated tip during the frictional process. Tunneling of the tribo-charge into the gap between WS2 and the underlying substrate results in a long lifetime, which is about 100 times longer than conventional triboelectric charges. Moreover, we observe a positive correlation between the layer number and resistance to charge dissipation. Our finding can become the driving force for a new category of two-dimensional (2D) WS2 triboelectrically controllable nanodevices.

Controllable Tunneling Triboelectrification of Two-Dimensional Chemical Vapor Deposited MoS2.

Tunneling triboelectrification of chemical vapor deposited monolayer MoS2 has been characterized at nanoscale with contact-mode atomic force microscopy (AFM) and Kelvin force microscopy (KFM). Although charges can be trapped on insulators like SiO2 by conventional triboelectrification, triboelectric charges tunneling through MoS2 and localized at the underlying substrate exhibit more than two orders of magnitude longer lifetime. Their polarity and density can be modified by triboelectric process with various bias voltages applied to Pt-coated AFM tips, and the saturated density is almost 30 times higher than the reported result of SiO2. Thus, the controllable tunneling triboelectric properties of MoS2 on insulating substrates can provide guidance to build a new class of two-dimensional (2D) MoS2-based nanoelectronic devices.

Mechanochromic Reconfigurable Metasurfaces.

The change of optical properties that some usually natural compounds or polymeric materials show upon the application of external stress is named mechanochromism. Herein, an artificial nanomechanical metasurface formed by a subwavelength nanowire array made of molybdenum disulfide, molybdenum oxide, and silicon nitride changes color upon mechanical deformation. The aforementioned deformation induces reversible changes in the optical transmission (relative transmission change of 197% at 654 nm), thus demonstrating a giant mechanochromic effect. Moreover, these types of metasurfaces can exist in two nonvolatile states presenting a difference in optical transmission of 45% at 678 nm, when they are forced to bend rapidly. The wide optical tunability that photonic nanomechanical metasurfaces, such as the one presented here, possess by design, can provide a valuable platform for mechanochromic and bistable responses across the visible and near infrared regime and form a new family of smart materials with applications in reconfigurable, multifunctional photonic filters, switches, and stress sensors.

Enhanced all-optical modulation in a graphene-coated fibre with low insertion loss.

Graphene is a highly versatile two-dimensional material platform that offers exceptional optical and electrical properties. Of these, its dynamic conductivity and low effective carrier mass are of particular interest for optoelectronic applications as they underpin the material's broadband nonlinear optical absorption and ultra-fast carrier mobility, respectively. In this paper, we utilize these phenomena to demonstrate a high-speed, in-fibre optical modulator developed on a side-polished optical fibre platform. An especially low insertion loss (<1 dB) was achieved by polishing the fibre to a near atomically smooth surface (<1 nm RMS), which minimized scattering and ensured excellent contact between the graphene film and the fibre. In order to enhance the light-matter interaction, the graphene film is coated with a high index polyvinyl butyral layer, which has the added advantage of acting as a barrier to the surrounding environment. Using this innovative approach, we have fabricated a robust and stable all-fibre device with an extinction ratio as high as 9 dB and operation bandwidth of 0.5 THz. These results represent a key step towards the integration of low-dimensional materials within standard telecoms networks.

Ultrafast carrier thermalization and cooling dynamics in few-layer MoS2.

Femtosecond optical pump-probe spectroscopy with 10 fs visible pulses is employed to elucidate the ultrafast carrier dynamics of few-layer MoS2. A nonthermal carrier distribution is observed immediately following the photoexcitation of the A and B excitonic transitions by the ultrashort, broadband laser pulse. Carrier thermalization occurs within 20 fs and proceeds via both carrier-carrier and carrier-phonon scattering, as evidenced by the observed dependence of the thermalization time on the carrier density and the sample temperature. The n(-0.37 ± 0.03) scaling of the thermalization time with carrier density suggests that equilibration of the nonthermal carrier distribution occurs via non-Markovian quantum kinetics. Subsequent cooling of the hot Fermi-Dirac carrier distribution occurs on the ∼ 0.6 ps time scale via carrier-phonon scattering. Temperature- and fluence-dependence studies reveal the involvement of hot phonons in the carrier cooling process. Nonadiabatic ab initio molecular dynamics simulations, which predict carrier-carrier and carrier-phonon scattering time scales of 40 fs and 0.5 ps, respectively, lend support to the assignment of the observed carrier dynamics.