A series of sila-annulated phenanthrene imides were synthesized through a three-step synthetic route, which represent a hybrid class of biphenyl-based π-conjugated molecules incorporating an imide unit and silole. A comprehensive investigation of their structural, photophysical, and electronic properties was studied by experiment and theoretical calculations. Notably, sila-annulated phenanthrene imides with significant aggregation-induced emission (AIE) properties were observed.
The exceptional electronic and photonic properties of the monolayers of transition metal dichalcogenides including the spin-orbit splitting of the valence and conduction bands at the K points of the Brillouin zone make them promising for novel applications in electronics, photonics and optoelectronics. Scalable growth of these materials and understanding of their interaction with the substrate is crucial for these applications. Here we report the growth of MoS2 and MoSe2 monolayers on Au(111) by chemical vapor deposition at ambient pressure as well as the analysis of their structural and electronic properties down to the atomic scale. To this aim, we apply ultrahigh vacuum surface sensitive techniques including scanning tunneling microscopy and spectroscopy, low-energy electron diffraction, X-ray and angle-resolved ultraviolet photoelectron spectroscopy in combination with Raman spectroscopy at ambient conditions. We demonstrate the growth of high-quality epitaxial single crystalline MoS2 and MoSe2 monolayers on Au(111) and show the impact of annealing on the monolayer/substrate interaction. Thus, as-grown and moderately annealed (<100 °C) MoSe2 monolayers are decoupled from the substrate by excess Se atoms, whereas annealing at higher temperatures (>250 °C) results in their strong coupling with the substrate caused by desorption of the excess Se. The MoS2 monolayers are strongly coupled to the substrate and the interaction remains almost unchanged even after annealing up to 450 °C.
Osteoporosis is one of the major health problems characterized by decreased bone density and increased risk of fractures. Nowadays, the treating strategies against osteoporosis are efficient, but still have some drawbacks. Micheliolide, a guaianolide sesquiterpene lactone isolated from Michelia compressa and Michelia champac, has been reported to have anti-inflammatory effects. Here, our data suggest that Micheliolide could protect mice from ovariectomy induced bone loss. According to the Micro-CT scan and histomorphometry quantification data, Micheliolide treatment inhibits excessive osteoclast bone resorption without affecting bone formation in estrogen deficiency mice. Consistently, our data suggest that Micheliolide could inhibit osteoclastogenesis in vitro. Additionally, we confirmed that Micheliolide inhibits osteoclasts formation via inhibiting P38 MAPK signaling pathway, and P79350 (a P38 agonist) could rescue this effect. In summary, our data suggest that Micheliolide could ameliorate estrogen deficiency-induced bone loss via attenuating osteoclastogenesis. Hence, Micheliolide could be used as a novel anti-resorptive agent against osteoporosis.
Bone Resorption , Osteoporosis , Female , Animals , Mice , Osteoclasts , Bone Resorption/drug therapy , Bone Resorption/prevention & control , Bone Resorption/etiology , Osteogenesis , Osteoporosis/drug therapy , Osteoporosis/etiology , Osteoporosis/prevention & control , Sesquiterpenes, Guaiane/pharmacology , Estrogens/pharmacology , Estrogens/metabolism , Cell Differentiation , Mice, Inbred C57BL
Being able to control the neutral excitonic flux is a mandatory step for the development of future room-temperature two-dimensional excitonic devices. Semiconducting Monolayer Transition Metal Dichalcogenides (TMD-ML) with extremely robust and mobile excitons are highly attractive in this regard. However, generating an efficient and controlled exciton transport over long distances is a very challenging task. Here we demonstrate that an atomically sharp TMD-ML lateral heterostructure (MoSe2-WSe2) transforms the isotropic exciton diffusion into a unidirectional excitonic flow through the junction. Using tip-enhanced photoluminescence spectroscopy (TEPL) and a modified exciton transfer model, we show a discontinuity of the exciton density distribution on each side of the interface. We introduce the concept of exciton Kapitza resistance, by analogy with the interfacial thermal resistance referred to as Kapitza resistance. By comparing different heterostructures with or without top hexagonal boron nitride (hBN) layer, we deduce that the transport properties can be controlled, over distances far greater than the junction width, by the exciton density through near-field engineering and/or laser power density. This work provides a new approach for controlling the neutral exciton flow, which is key toward the conception of excitonic devices.
The orientation and ellipticity of terahertz (THz) polarization generated by a two-color strong field not only casts light on underlying mechanisms of laser-matter interaction, but also plays an important role for various applications. We develop the Coulomb-corrected classical trajectory Monte Carlo (CTMC) method to well reproduce the joint measurements, that the THz polarization generated by the linearly polarized 800 nm and circularly polarized 400 nm fields is independent on two-color phase delay. The trajectory analysis shows that the Coulomb potential twists the THz polarization by deflecting the orientation of asymptotic momentum of electron trajectories. Further, the CTMC calculations predict that, the two-color mid-infrared field can effectively accelerate the electron rapidly away from the parent core to relieve the disturbance of Coulomb potential, and simultaneously create large transverse acceleration of trajectories, leading to the circularly polarized THz radiation.
The existence of bound charge transfer (CT) excitons at the interface of monolayer lateral heterojunctions has been debated in literature, but contrary to the case of interlayer excitons in vertical heterostructure their observation still has to be confirmed. Here, we present a microscopic study investigating signatures of bound CT excitons in photoluminescence spectra at the interface of hBN-encapsulated lateral MoSe2-WSe2 heterostructures. Based on a fully microscopic and material-specific theory, we reveal the many-particle processes behind the formation of CT excitons and how they can be tuned via interface- and dielectric engineering. For junction widths smaller than the Coulomb-induced Bohr radius we predict the appearance of a low-energy CT exciton. The theoretical prediction is compared with experimental low-temperature photoluminescence measurements showing emission in the bound CT excitons energy range. We show that for hBN-encapsulated heterostructures, CT excitons exhibit small binding energies of just a few tens meV and at the same time large dipole moments, making them promising materials for optoelectronic applications (benefiting from an efficient exciton dissociation and fast dipole-driven exciton propagation). Our joint theory-experiment study presents a significant step towards a microscopic understanding of optical properties of technologically promising 2D lateral heterostructures.
Experimental results on the charge-state-dependent sputtering of metallic gold nanoislands are presented. Irradiations with slow highly charged ions of metallic targets were previously considered to show no charge state dependent effects on ion-induced material modification, since these materials possess enough free electrons to dissipate the deposited potential energy before electron-phonon coupling can set in. By reducing the size of the target material down to the nanometer regime and thus enabling a geometric energy confinement, a possibility is demonstrated to erode metallic surfaces by charge state related effects in contrast to regular kinetic sputtering.
Stacked hetero-structures of two-dimensional materials allow for a design of interactions with corresponding electronic and mechanical properties. We report structure, work function, and frictional properties of 1 to 4 layers of MoS2 grown by chemical vapor deposition on epitaxial graphene on SiC(0001). Experiments were performed by atomic force microscopy in ultra-high vacuum. Friction is dominated by adhesion which is mediated by a deformation of the layers to adapt the shape of the tip apex. Friction decreases with increasing number of MoS2 layers as the bending rigidity leads to less deformation. The dependence of friction on applied load and bias voltage can be attributed to variations in the atomic potential corrugation of the interface, which is enhanced by both load and applied bias. Minimal friction is obtained when work function differences are compensated.
High-harmonic generation (HHG) in solids has been touted as a way to probe ultrafast dynamics and crystal symmetries in condensed matter systems. Here, we investigate the polarization properties of high-order harmonics generated in monolayer MoS_{2}, as a function of crystal orientation relative to the mid-infrared laser field polarization. At several different laser wavelengths we experimentally observe a prominent angular shift of the parallel-polarized odd harmonics for energies above approximately 3.5 eV, and our calculations indicate that this shift originates in subtle differences in the recombination dipole strengths involving multiple conduction bands. This observation is material specific and is in addition to the angular dependence imposed by the dynamical symmetry properties of the crystal interacting with the laser field, and may pave the way for probing the vectorial character of multiband recombination dipoles.
We measured the exciton dynamics in van der Waals heterojunctions of transition metal dichalcogenides (TMDCs) and organic semiconductors (OSs). TMDCs and OSs are semiconducting materials with rich and highly diverse optical and electronic properties. Their heterostructures, exhibiting van der Waals bonding at their interfaces, can be utilized in the field of optoelectronics and photovoltaics. Two types of heterojunctions, MoS2-pentacene and WSe2-pentacene, were prepared by layer transfer of 20 nm pentacene thin films as well as MoS2 and WSe2 monolayer crystals onto Au surfaces. The samples were studied by means of transient absorption spectroscopy in the reflectance mode. We found that A-exciton decay by hole transfer from MoS2 to pentacene occurs with a characteristic time of 21 ± 3 ps. This is slow compared to previously reported hole transfer times of 6.7 ps in MoS2-pentacene junctions formed by vapor deposition of pentacene molecules onto MoS2 on SiO2. The B-exciton decay in WSe2 shows faster hole transfer rates for WSe2-pentacene heterojunctions, with a characteristic time of 7 ± 1 ps. The A-exciton in WSe2 also decays faster due to the presence of a pentacene overlayer; however, fitting the decay traces did not allow for the unambiguous assignment of the associated decay time. Our work provides important insights into excitonic dynamics in the growing field of TMDC-OS heterojunctions.
We compare the ion-induced electron emission from freestanding monolayers of graphene and MoS_{2} to find a sixfold higher number of emitted electrons for graphene even though both materials have similar work functions. An effective single-band Hubbard model explains this finding by a charge-up in MoS_{2} that prevents low energy electrons from escaping the surface within a period of a few femtoseconds after ion impact. We support these results by measuring the electron energy distribution for correlated pairs of electrons and transmitted ions. The majority of emitted primary electrons have an energy below 10 eV and are therefore subject to the dynamic charge-up effects at surfaces.
A simple, large area, and cost-effective soft lithographic method is presented for the patterned growth of high-quality 2D transition metal dichalcogenides (TMDs). Initially, a liquid precursor (Na2 MoO4 in an aqueous solution) is patterned on the growth substrate using the micromolding in capillaries technique. Subsequently, a chemical vapor deposition step is employed to convert the precursor patterns to monolayer, few layers, or bulk TMDs, depending on the precursor concentration. The grown patterns are characterized using optical microscopy, atomic force microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and photoluminescence spectroscopy to reveal their morphological, chemical, and optical characteristics. Additionally, electronic and optoelectronic devices are realized using the patterned TMDs and tested for their applicability in field effect transistors and photodetectors. The photodetectors made of MoS2 line patterns show a very high responsivity of 7674 A W-1 and external quantum efficiency of 1.49 × 106 %. Furthermore, the multiple grain boundaries present in patterned TMDs enable the fabrication of memtransistor devices. The patterning technique presented here may be applied to many other TMDs and related heterostructures, potentially advancing the fabrication of TMDs-based device arrays.
One-pot chemical vapor deposition (CVD) growth of large-area Janus SeMoS monolayers is reported, with the asymmetric top (Se) and bottom (S) chalcogen atomic planes with respect to the central transition metal (Mo) atoms. The formation of these 2D semiconductor monolayers takes place upon the thermodynamic-equilibrium-driven exchange of the bottom Se atoms of the initially grown MoSe2 single crystals on gold foils with S atoms. The growth process is characterized by complementary experimental techniques including Raman and X-ray photoelectron spectroscopy, transmission electron microscopy, and the growth mechanisms are rationalized by first principle calculations. The remarkably high optical quality of the synthesized Janus monolayers is demonstrated by optical and magneto-optical measurements which reveal the strong exciton-phonon coupling and enable an exciton g-factor of -3.3.
Mixed-dimensional hybrid structures have recently gained increasing attention as promising building blocks for novel electronic and optoelectronic devices. In this context, hybridization of semiconductor nanowires with two-dimensional materials could offer new ways to control and modulate lasing at the nanoscale. In this work, we deterministically fabricate hybrid mixed-dimensional heterostructures composed of ZnO nanowires and MoS2 monolayers with micrometer control over their relative position. First, we show that our deterministic fabrication method does not degrade the optical properties of the ZnO nanowires. Second, we demonstrate that the lasing wavelength of ZnO nanowires can be tuned by several nanometers by hybridization with CVD-grown MoS2 monolayers. We assign this spectral shift of the lasing modes to an efficient carrier transfer at the heterointerface and the subsequent increase of the optical band gap in ZnO (Moss-Burstein effect).
We studied the energy-level alignment at interfaces between various transition-metal dichalcogenide (TMD) monolayers, MoS2, MoSe2, WS2, and WSe2, and metal electrodes with different work functions (WFs). TMDs were deposited on SiO2/silicon wafers by chemical vapor deposition and transferred to Al and Au substrates, with significantly different WFs to identify the metal-semiconductor junction behavior: oxide-terminated Al (natural oxidation) and Au (UV-ozone oxidation) with a WF difference of 0.8 eV. Kelvin probe force microscopy was employed for this study, based on which electronic band diagrams for each case were determined. We observed the Fermi-level pinning for MoS2, while WSe2/metal junctions behaved according to the Schottky-Mott limit. WS2 and MoSe2 exhibited intermediate behavior.
Atomically thin transition metal dichalcogenides are highly promising for integrated optoelectronic and photonic systems due to their exciton-driven linear and nonlinear interactions with light. Integrating them into optical fibers yields novel opportunities in optical communication, remote sensing, and all-fiber optoelectronics. However, the scalable and reproducible deposition of high-quality monolayers on optical fibers is a challenge. Here, the chemical vapor deposition of monolayer MoS2 and WS2 crystals on the core of microstructured exposed-core optical fibers and their interaction with the fibers' guided modes are reported. Two distinct application possibilities of 2D-functionalized waveguides to exemplify their potential are demonstrated. First, the excitonic 2D material photoluminescence is simultaneously excited and collected with the fiber modes, opening a novel route to remote sensing. Then it is shown that third-harmonic generation is modified by the highly localized nonlinear polarization of the monolayers, yielding a new avenue to tailor nonlinear optical processes in fibers. It is anticipated that the results may lead to significant advances in optical-fiber-based technologies.
In this work, Ti and Mg alloys were made into composites by using spark plasma sintering, in order to combine the high stiffness of Ti and biodegradability of Mg alloys. The effect of the content of Mg-3Zn alloy on the degradability was studied by using electrochemical corrosion, immersion in simulated body fluid and incubation of Saos-2â¯cells. The results show that Ti-Mg metal-metal composites (MMCs) exhibit low Young's modulus (31-48â¯GPa) and good yield strength (616.5-642.8â¯MPa). The modulus and strength both decrease with the content of Mg-3Zn alloy increasing. The electrochemical corrosion rates of Ti-Mg MMCs were much lower than that of monolithic Mg-3Zn alloys. After an immersion for 21 days, Ti matrix remained integrity and Mg phase dissolved in the solution, inducing the formation of apatite layer on the MMCs. The precipitation of apatite increased with the content of Mg-3Zn alloy increasing. In vitro study indicated that Ti-10Mg and Ti-20â¯Mgâ¯MMCs possessed good biocompatibility to Saos-2â¯cells, while the biocompatibility of Ti-30â¯Mgâ¯MMCs decreased slightly. In summary, Ti-Mg MMCs are promising implant materials with adjustable degradation rates and improved biocompatibility for orthopedic applications.
Alloys/chemistry , Biocompatible Materials/chemistry , Apatites/chemistry , Biocompatible Materials/pharmacokinetics , Cell Line , Cell Survival/drug effects , Compressive Strength , Corrosion , Humans , Magnesium/chemistry , Materials Testing , Spectroscopy, Fourier Transform Infrared , Titanium/chemistry , X-Ray Diffraction
We propose a novel scheme to realize an optical waveguide induced by an active Raman gain (ARG) process in a four-level N-type atomic system. Because of the nature of the ARG, there are two distinct features related to the waveguide: i) It is not absorptive, on the contrary, weak gain is presented; ii) It can be improved by the Doppler effect in the sense that the dispersion is enhanced while the gain is further reduced. This is in sharp contrast to the previously considered schemes where usually the optical induced waveguide is passive and is severely attenuated by the Doppler effect. We then study the paraxial light propagation in the waveguide which shows that the propagation dynamics is lossless and diffractionless.
