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Monolayer transition metal dichalcogenides (TMDs) have emerged as promising materials to generate single-photon emitters (SPEs). While there are several previous reports in the literature about TMD-based SPEs, the precise nature of the excitonic states involved in them is still under debate. Here, we use magneto-optical techniques under in-plane and out-of-plane magnetic fields to investigate the nature of SPEs in WSe2 monolayers on glass substrates under different strain profiles. Our results reveal important changes on the exciton localization and, consequently, on the optical properties of SPEs. Remarkably, we observe an anomalous PL energy redshift with no significant changes of photoluminescence (PL) intensity under an in-plane magnetic field. We present a model to explain this redshift based on intervalley defect excitons under a parallel magnetic field. Overall, our results offer important insights into the nature of SPEs in TMDs, which are valuable for future applications in quantum technologies.
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We report experimental investigations of spin-to-charge current conversion and charge transfer (CT) dynamics at the interface of the graphene/WS2 van der Waals heterostructure. Pure spin current was produced by the spin precession in the microwave-driven ferromagnetic resonance of a permalloy film (Py=Ni81Fe19) and injected into the graphene/WS2 heterostructure through a spin pumping process. The observed spin-to-charge current conversion in the heterostructure is attributed to the inverse Rashba-Edelstein effect (IREE) at the graphene/WS2 interface. Interfacial CT dynamics in this heterostructure was investigated based on the framework of the core-hole clock (CHC) approach. The results obtained from spin pumping and CHC studies show that the spin-to-charge current conversion and charge transfer processes are more efficient in the graphene/WS2 heterostructure compared to isolated WS2 and graphene films. The results show that the presence of WS2 flakes improves the current conversion efficiency. These experimental results are corroborated by density functional theory (DFT) calculations, which reveal (i) Rashba spin-orbit splitting of graphene orbitals and (ii) electronic coupling between graphene and WS2 orbitals. This study provides valuable insights for optimizing the design and performance of spintronic devices.
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The goal of the sensor industry is to develop innovative, energy-efficient, and reliable devices to detect molecules relevant to economically important sectors such as clinical diagnoses, environmental monitoring, food safety, and wearables. The current demand for portable, fast, sensitive, and high-throughput platforms to detect a plethora of new analytes is continuously increasing. The 2D transition metal dichalcogenides (2D-TMDs) are excellent candidates to fully meet the stringent demands in the sensor industry; 2D-TMDs properties, such as atomic thickness, large surface area, and tailored electrical conductivity, match those descriptions of active sensor materials. However, the detection capability of 2D-TMDs is limited by their intrinsic tendency to aggregate and settle, which reduces the surface area available for detection, in addition to the weak interactions that pristine 2D-TMDs normally exhibit with analytes. Chemical functionalization has been proposed as a consensus solution to these limitations. Tailored surface modification of 2D-TMDs, either by covalent functionalization, non-covalent functionalization, or a mixture of both, allows for improved specificity of the surface-analyte interaction while reducing van der Waals forces between 2D-TMDs avoiding agglomeration and precipitation. From this perspective, we review the recent advances in improving the detection of biomolecules, heavy metals, and gases using chemically functionalized 2D-TMDs. Covalent and non-covalent functionalized 2D-TMDs are commonly used for the detection of biomolecules and metals, while 2D-TMDs functionalized with metal nanoparticles are used for gas and Raman sensors. Finally, we describe the limitations and further strategies that might pave the way for miniaturized, flexible, smart, and low-cost sensing devices.
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van der Waals heterostructures composed of two-dimensional (2D) transition metal dichalcogenides and vdW magnetic materials offer an intriguing platform to functionalize valley and excitonic properties in nonmagnetic TMDs. Here, we report magneto photoluminescence (PL) investigations of monolayer (ML) MoSe2 on the layered A-type antiferromagnetic (AFM) semiconductor CrSBr under different magnetic field orientations. Our results reveal a clear influence of the CrSBr magnetic order on the optical properties of MoSe2, such as an anomalous linear-polarization dependence, changes of the exciton/trion energies, a magnetic-field dependence of the PL intensities, and a valley g-factor with signatures of an asymmetric magnetic proximity interaction. Furthermore, first-principles calculations suggest that MoSe2/CrSBr forms a broken-gap (type-III) band alignment, facilitating charge transfer processes. The work establishes that antiferromagnetic-nonmagnetic interfaces can be used to control the valley and excitonic properties of TMDs, relevant for the development of opto-spintronics devices.
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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.
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Researchers in cancer nanomedicine are exploring a revolutionary multifaceted carrier for treatment and diagnosis, resulting in the proposal of various drug cargos or "magic bullets" in this past decade. Even though different nano-based complexes are registered for clinical trials, very few products enter the final stages each year because of various issues. This prevents the formulations from entering the market and being accessible to patients. In the search for novel materials, the exploitation of 2D nanosheets, including but not limited to the highly acclaimed graphene, has created extensive interest for biomedical applications. A unique set of properties often characterize 2D materials, including semiconductivity, high surface area, and their chemical nature, which allow simple decoration and functionalization procedures, structures with high stability and targeting properties, vectors for controlled and sustained release of drugs, and materials for thermal-based therapies. This review discusses the challenges and opportunities of recently discovered 2D nanosheets for cancer therapeutics, with special attention paid to the most promising design technologies and their potential for clinical translation in the future.
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Vacancies in materials structureâlowering its atomic densityâtake the system closer to the atomic limit, to which all systems are topologically trivial. Here we show a mechanism of mediated interaction between vacancies inducing a topologically nontrivial phase. Within an ab initio approach we explore topological transition dependence with the vacancy density in transition metal dichalcogenides. As a case of study, we focus on the PtSe2, for which the pristine form is a trivial semiconductor with an energy gap of 1.2 eV. The vacancies states lead to a large topological gap of 180 meV within the pristine system gap. We derive an effective model describing this topological phase in other transition metal dichalcogenide systems. The mechanism driving the topological phase allows the construction of backscattering protected metallic channels embedded in a semiconducting host.
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The Stark effect is one of the most efficient mechanisms to manipulate many-body states in nanostructured systems. In mono- and few-layer transition metal dichalcogenides, it has been successfully induced by optical and electric field means. Here, we tune the optical emission energies and dissociate excitonic states in MoSe2 monolayers employing the 220 MHz in-plane piezoelectric field carried by surface acoustic waves. We transfer the monolayers to high dielectric constant piezoelectric substrates, where the neutral exciton binding energy is reduced, allowing us to efficiently quench (above 90%) and red-shift the excitonic optical emissions. A model for the acoustically induced Stark effect yields neutral exciton and trion in-plane polarizabilities of 530 and 630 × 10-5 meV/(kV/cm)2, respectively, which are considerably larger than those reported for monolayers encapsulated in hexagonal boron nitride. Large in-plane polarizabilities are an attractive ingredient to manipulate and modulate multiexciton interactions in two-dimensional semiconductor nanostructures for optoelectronic applications.
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In the search for gas sensing materials, two-dimensional materials offer the possibility of designing sensors capable of tuning the electronic band structure by controlling their thickness, quantity of dopants, alloying between different materials, vertical stacking, and the presence of gases. Through materials engineering it is feasible to study the electrical properties of two-dimensional materials which are directly related to their crystalline structure, first Brillouin zone, and dispersion energy, the latter estimated through the tight-binding model. A review of the electrical properties directly related to the crystalline structure of these materials is made in this article for the two-dimensional materials used in the design of gas sensors. It was found that most 2D sensing materials have a hexagonal crystalline structure, although some materials have monoclinic, orthorhombic and triclinic structures. Through the simulation of the mathematical models of the dispersion energy, two-dimensional and three-dimensional electronic band structures were predicted for graphene, hexagonal boron nitride (h-BN) and silicene, which must be known before designing a gas sensor.
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Resonant Raman spectroscopy is a powerful tool for providing information about excitons and exciton-phonon coupling in two-dimensional materials. We present here resonant Raman experiments of single-layered WS2 and WSe2 using more than 25 laser lines. The Raman excitation profiles of both materials show unexpected differences. All Raman features of WS2 monolayers are enhanced by the first-optical excitations (with an asymmetric response for the spin-orbit related XA and XB excitons), whereas Raman bands of WSe2 are not enhanced at XA/B energies. Such an intriguing phenomenon is addressed by DFT calculations and by solving the Bethe-Salpeter equation. These two materials are very similar. They prefer the same crystal arrangement, and their electronic structure is akin, with comparable spin-orbit coupling. However, we reveal that WS2 and WSe2 exhibit quite different exciton-phonon interactions. In this sense, we demonstrate that the interaction between XC and XA excitons with phonons explains the different Raman responses of WS2 and WSe2, and the absence of Raman enhancement for the WSe2 modes at XA/B energies. These results reveal unusual exciton-phonon interactions and open new avenues for understanding the two-dimensional materials physics, where weak interactions play a key role coupling different degrees of freedom (spin, optic, and electronic).
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Resonant Raman spectroscopy (RRS) is a very useful tool to study physical properties of materials since it provides information about excitons and their coupling with phonons. We present in this work a RRS study of samples of WSe2 with one, two, and three layers (1L, 2L, and 3L), as well as bulk 2H-WSe2, using up to 20 different laser lines covering the visible range. The first- and second-order Raman features exhibit different resonant behavior, in agreement with the double (and triple) resonance mechanism(s). From the laser energy dependence of the Raman intensities (Raman excitation profile, or REP), we obtained the energies of the excited excitonic states and their dependence with the number of atomic layers. Our results show that Raman enhancement is much stronger for the excited A' and B' states, and this result is ascribed to the different exciton-phonon coupling with fundamental and excited excitonic states.