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Heterostructures (HSs) formed by the transition-metal dichalcogenide materials have shown great promise in next-generation (opto)electronic applications. An artificially twisted HS allows us to manipulate the optical and electronic properties. In this work, we introduce the understanding of the energy transfer (ET) process governed by the dipolar interaction in a twisted molybdenum diselenide (MoSe2) homobilayer without any charge-blocking interlayer. We fabricated an unconventional homobilayer (i.e., HS) with a large twist angle (â¼57°) by combining the chemical vapor deposition (CVD) and mechanical exfoliation (Exf.) techniques to fully exploit the lattice parameter mismatch and indirect/direct (CVD/Exf.) bandgap nature. These effectively weaken the interlayer charge transfer and allow the ET to control the carrier recombination channels. Our experimental and theoretical results explain a massive HS photoluminescence enhancement due to an efficient ET process. This work shows that the electronically decoupled MoSe2 homobilayer is coupled by the ET process, mimicking a "true" heterobilayer nature.
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Inducing immunogenic cell death (ICD) during photothermal therapy (PTT) has the potential to effectively trigger photothermal immunotherapy (PTI). However, ICD induced by PTT alone is often limited by inefficient PTT, low immunogenicity of tumor cells, and a dysregulated redox microenvironment. Herein, we develop MoSe2 nanosheets with high-percentage metallic 1T phase and rich exposed active Mo centers through phase and defect engineering of MoSe2 as an effective nanoagent for PTI. The metallic 1T phase in MoSe2 nanosheets endows them with strong PTT performance, and the abundant exposed active Mo centers endow them with high activity for glutathione (GSH) depletion. The MoSe2-mediated high-performance PTT synergizing with efficient GSH depletion facilitates the release of tumor-associated antigens to induce robust ICD, thus significantly enhancing checkpoint blockade immunotherapy and activating systemic immune response in mouse models of colorectal cancer and triple-negative metastatic breast cancer.
Assuntos
Imunoterapia , Molibdênio , Terapia Fototérmica , Animais , Camundongos , Imunoterapia/métodos , Humanos , Molibdênio/química , Feminino , Linhagem Celular Tumoral , Nanoestruturas/química , Nanoestruturas/uso terapêutico , Glutationa/química , Glutationa/metabolismo , Neoplasias Colorretais/terapia , Neoplasias Colorretais/patologia , Neoplasias Colorretais/imunologia , Morte Celular Imunogênica/efeitos dos fármacos , Neoplasias de Mama Triplo Negativas/terapia , Neoplasias de Mama Triplo Negativas/imunologia , Neoplasias de Mama Triplo Negativas/patologia , Raios Infravermelhos , Selênio/química , Selênio/uso terapêutico , Fototerapia/métodosRESUMO
Transition metal dichalcogenides (TMDCs) have garnered considerable interest over the past decade as a class of semiconducting layered materials. Most studies on the carrier dynamics in these materials have focused on the monolayer due to its direct bandgap, strong photoluminescence, and strongly bound excitons. However, a comparative understanding of the carrier dynamics in multilayer (e.g., >10 layers) flakes is still absent. Recent computational studies have suggested that excitons in bulk TMDCs are confined to individual layers, leading to room-temperature stable exciton populations. Using this new context, we explore the carrier dynamics in MoSe2 flakes that are between â¼16 and â¼125 layers thick. We assign the kinetics to exciton-exciton annihilation (EEA) and Shockley-Read-Hall recombination of free carriers. Interestingly, the average observed EEA rate constant (0.003 cm2/s) is nearly independent of flake thickness and 2 orders of magnitude smaller than that of an unencapsulated monolayer (0.33 cm2/s) but very similar to values observed in encapsulated monolayers. Thus, we posit that strong intralayer interactions minimize the effect of layer thickness on recombination dynamics, causing the multilayer to behave like the monolayer and exhibit an apparent EEA rate intrinsic to MoSe2.
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We demonstrate the integration of a thin BaTiO3 (BTO) membrane with monolayer MoSe2 in a dual-gate device that enables in situ manipulation of the BTO ferroelectric polarization with a voltage pulse. While two-dimensional (2D) transition metal dichalcogenides (TMDs) offer remarkable adaptability, their hybrid integration with other families of functional materials beyond the realm of 2D materials has been challenging. Released functional oxide membranes offer a solution for 2D/3D integration via stacking. 2D TMD excitons can serve as a local probe of the ferroelectric polarization in BTO at a heterogeneous interface. Using photoluminescence (PL) of MoSe2 excitons to optically read out the doping level, we find that the relative population of charge carriers in MoSe2 depends sensitively on the ferroelectric polarization. This finding points to a promising avenue for future-generation versatile sensing devices with high sensitivity, fast readout, and diverse applicability for advanced signal processing.
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Transition metal dichalcogenides (TMDs) are promising 2D nanomaterials for diverse applications, but their intrinsic chemical inertness hinders their modification. Herein, a novel approach is presented for the photocatalytic acylation of 2H-MoS2 and 2H-MoSe2, utilizing tetrabutyl ammonium decatungstate ((nBu4N)4W10O32) polyoxometalate complex as a catalyst and a conventional halogen lamp as a source of irradiation. By harnessing the semiconducting properties of TMDs, new avenues emerge for the functionalization of these materials. This novel photocatalytic protocol constitutes the first report on the chemical modification of 2D nanomaterials based on a catalytic protocol and applies to both aliphatic and aromatic substrates. The scope of the decatungstate-photocatalyzed acylation reaction of TMDs is explored by employing an alkyl and an aromatic aldehyde and the success of the methodology is confirmed by diverse spectroscopic, thermal, microscopy imaging, and redox techniques. This catalytic approach on modifying 2D nanomaterials introduces the principles of atom economy in a functionalization protocol for TMDs. It marks a transformative shift toward more sustainable and efficient methodologies in the realm of TMD modification and nanomaterial chemistry.
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The development of lithium-sulfur batteries is seriously hindered by the shuttle effect of lithium polysulfides (LiPSs) and the low electrical conductivity of sulfur. To solve these problems, efficient catalysts can be used to improve the conversion rate of LiPSs and the conductivity of sulfur cathode. Herein, annealed melamine foam supported MoSe2 (NCF@MoSe2) is used as interlayer and the MoSe2/MoP heterojunction obtained by phosphating MoSe2 is further used as the catalyst material for metal fusion with a sulfur element. The interlayer can not only improve the electrical conductivity and effectively adsorb and catalyze LiPSs, but more importantly, the MoSe2/MoP heterojunction can also effectively adsorb and catalyze LiPSs, so that the batteries have a dual inhibition shuttling effect strategy. Furthermore, the rapid anchor-diffusion transition of LiPSs, and the suppression of shuttling effects by catalyst materials are elucidated using theoretical calculations and in situ Raman spectroscopy. The two-step catalytic strategy exhibits a high reversibility of 983 mAh g-1 after 200 cycles at 0.5 C and a high-rate capacity of 889 mAh g-1 at 5 C. This work provides a feasible solution for the rational design of interlayer and heterojunction materials and is also conducive to the development of more advanced Li-S batteries.
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1T-MoSe2 is recognized as a promising anode material for sodium-ion batteries, thanks to its excellent electrical conductivity and large interlayer distance. However, its inherent thermodynamic instability often presents unparalleled challenges in phase control and stabilization. Here, a molecular intercalation strategy is developed to synthesize thermally stable 1T-rich MoSe2, covalently bonded to an intercalated carbon layer (1TR/2H-MoSe2@C). Density functional theory calculations uncover that the introduced ethylene glycol molecules not only serve as electron donors, inducing a reorganization of Mo 4d orbitals, but also as sacrificial guest materials that generate a conductive carbon layer. Furthermore, the CâSe/CâOâMo bonds encourage strong interfacial electronic coupling, and the carbon layer prevents the restacking of MoSe2, regulating the maximum 1T phase to an impressive 80.3%. Consequently, the 1TR/2H-MoSe2@C exhibits an extraordinary rate capacity of 326 mAh g-1 at 5 A g-1 and maintains a long-term cycle stability up to 1500 cycles, with a capacity of 365 mAh g-1 at 2 A g-1. Additionally, the full cell delivers an appealing energy output of 194 Wh kg-1 at 208 W kg-1, with a capacity retention of 87.3% over 200 cycles. These findings contribute valuable insights toward the development of innovative transition metal dichalcogenides for next-generation energy storage technologies.
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The principal challenges faced by sodium-ion batteries (SIBs) and potassium-ion batteries (KIBs) revolve around identifying suitable host materials capable of accommodating metal ions with larger dimensions and addressing the issue of sluggish chemical kinetics. Herein, a MoSe2/Cr2Se3 heterojunction uniformly embedded is fabricated in nitrogen-doped hollow carbon nanospheres (MoSe2/Cr2Se3@N-HCSs) as an electrode material for SIBs and KIBs. Cr2Se3 exhibits spontaneous antiparallel alignment of magnetic moments. Mo2+ doping is employed to regulate the electron spin states of Cr2Se3. Moreover, the MoSe2 and Cr2Se3 heterojunctions induce a lattice mismatch at the heterostructure interface, resulting in spin-polarized states or localized magnetic moments at the interface, potentially contributing to spin-polarized surface capacitance. MoSe2/Cr2Se3@N-HCSs demonstrate a high capacity of 498 mAh g-1 at 0.1 A g-1 with good cycling stability (capacity of 405 mAh g-1 and a coulombic efficiency of 99.8% after 1000 cycles). Additionally, density functional theory (DFT) calculations simulate the accumulation of spin-polarized charges at the MoSe2/Cr2Se3@N-HCSs heterojunction interface, dependent on the surface electron density of the antiferromagnetic Cr2Se3 and the surface spin polarization near the Fermi level. After regulating the electron spin states through Mo-doping, the band gap of the material decreases. These significant findings provide novel insights into the design and synthesis of electrode materials with exceptional performance characteristics for batteries.
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Li-O2 batteries could deliver ultra-high theoretical energy density compared to current Li-ion batteries counterpart. The slow cathode reaction kinetics in Li-O2 batteries, however, limits their electrocatalytic performance. To this end, MoSe2 and Ni0.85 Se nanoflakes were decorated in carbon hollow nanoflowers, which were served as the cathode catalysts for Li-O2 batteries. The hexagonal Ni0.85 Se and MoSe2 show good structural compatibility with the same space group, resulting in a stable heterogeneous structure. The synergistic interaction of the unsaturated atoms and the built-in electric fields on the heterogeneous structure exposes abundant catalytically active sites, accelerating ion and charge transport and imparting superior electrochemical activity, including high specific capacities and stable cycling performance. More importantly, the lattice distances of the Ni0.85 Se (101) plane and MoSe2 (100) plane at the heterogeneous interfaces are highly matched to that of Li2 O2 (100) plane, facilitating epitaxial growth of Li2 O2 , as well as the formation and decomposition of discharge products during the cycles. This strategy of employing nonstoichiometric compounds to build heterojunctions and improve Li-O2 battery performance is expected to be applied to other energy storage or conversion systems.
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Currently, the only thermoelectric (TE) materials commercially available at room temperature are those based on bismuth telluride. However, their widespread application is limited due to their inferior thermoelectric and mechanical properties. In this study, a strategy of growing a rigid second phase of MoSe2 is employed, in situ within the matrix phase to achieve n-type bismuth telluride-based materials with exceptional mechanical and thermoelectric properties. The in situ grown second phase contributes to both the electronic and lattice thermal conductivities. This is primarily attributed to the strong energy filtering effect, as the second phase forms a semi-common lattice interfacial structure with the matrix phase during growth. Furthermore, for composites containing 2 wt% MoSe2, a maximum zT value of 1.24 at 373 K can be achieved. On this basis, 8-pair TE module is fabricated and 1-pair TE module is optimized using a homemade p-type material. The optimized 1-pair TE module generates a maximum output power of 13.6 µW, which is twice that of the 8-pair TE module and four times more than the 8-pair TE module fabricated by commercial material. This work facilitates the development of the TE module by presenting a novel approach to obtaining bismuth telluride-based thermoelectric materials with superior thermoelectric and mechanical properties.
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The exploitation of multicomponent composites (MCCs) has become the main pathway for obtaining advanced microwave absorption materials (MAMs). Herein, a metal valence state modulation strategy is proposed to tune the electromagnetic (EM) parameters and improve microwave absorption performances. Core@shell hollow carbon microspheres@MoSe2 and hollow carbon microspheres@MoSe2/MoOx MCCs with various mixed-valence states content are well-designed and produced by a simple hydrothermal reaction or/and heat treatment process. The results reveal that the thermal treatment of hollow carbon microspheres@MoSe2 in Ar and Ar/H2 leads to the in situ formation of MoOx and multivalence state, respectively, and the enhanced content of Mo4+ in the designed MCCs greatly boosts their impedance matching characteristics, polarization, and conduction loss capacities, which lead to their evidently improved EM wave absorption properties. Amongst, the as-prepared hollow carbon microspheres@MoSe2/MoOx MCCs achieve an effective absorption bandwidth of 5.80 GHz under a matching thickness of 1.97 mm and minimum reflection loss of -21.49 dB. Therefore, this work offers a simple and universal method to fabricate core@shell hollow carbon microspheres@MoSe2/MoOx MCCs, and a novel and feasible metal valence state modulation strategy is proposed to develop high-efficiency MAMs.
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Realizing n- and p-type transition metal dichalcogenide (TMD)-based field-effect transistors for nanoscale complementary metal oxide semiconductor (CMOS) applications remains challenging owing to undesirable contact resistance. Quantumtransport calculations were performed by replacing single-sided Se atoms of TMD near the interface with As or Br atoms to further improve the contact resistance. Here, partial selenium replacement produced a novel interface with a segment of metamaterial MoSeX (Pt/MoSeX/MoSe2; X = As, Br). Such stable metamaterials exhibit semi-metallicity, and the contact resistance can be thus lowered. Our findings provide insights into the potential of MoSe2-based nano-CMOS logic devices.
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Transition metal dichalcogenides (TMDs) with a two-dimensional (2D) structure and semiconducting features are highly favorable for the production of NH3gas sensors. Among the TMD family, WS2, WSe2, MoS2, and MoSe2exhibit high conductivity and a high surface area, along with high availability, reasons for which they are favored in gas-sensing studies. In this review, we have discussed the structure, synthesis, and NH3sensing characteristics of pristine, decorated, doped, and composite-based WS2, WSe2, MoS2, and MoSe2gas sensors. Both experimental and theoretical studies are considered. Furthermore, both room temperature and higher temperature gas sensors are discussed. We also emphasized the gas-sensing mechanism. Thus, this review provides a reference for researchers working in the field of 2D TMD gas sensors.
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The field-effect transistor (FET) is a fundamental component of semiconductors and the electronic industry. High on-current and mobility with layer-dependent features are required for outstanding FET channel material. Two-dimensional materials are advantageous over bulk materials owing to their higher mobility, high ON/OFF ratio, low tunneling current, and leakage problems. Moreover, two-dimensional heterostructures provide a better way to tune electrical properties. In this work, the two distinct possibilities of PdSe2/MoSe2heterostructure have been employed through mechanical exfoliation and analyzed their electrical response. These diffe approaches to heterostructure formation serve as crucial components of our investigation, allowing us to explore and evaluate the unique electronic properties arising from each design. This work demonstrates that the heterostructure possesses a better ON/OFF ratio of â¼5.78 × 105, essential in switching characteristics. Moreover, MoSe2provides a defect-free interface to PdSe2, resulting in a higher ON current of â¼10µA and mobility of â¼63.7 cm2V-1s-1, necessary for transistor applications. In addition, comprehending the process of charge transfer occurring at the interface between transition metal dichalcogenides is fundamental for advancing next-generation technologies. This work provides insights into the interface formed between the PdSe2and MoSe2that can be harnessed in transistor applications.
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An atomic-scale ripple structure has been revealed by electron tomography based on sequential projected atomic-resolution images, but it requires harsh imaging conditions with negligible structure evolution of the imaged samples. Here, we demonstrate that the ripple structure in monolayer MoSe2 can be facilely reconstructed from a single-frame scanning transmission electron microscopy (STEM) image collected at designated collection angles. The intensity and shape of each Se2 atomic column in the single-frame projected STEM image are synergistically combined to precisely map the slight misalignments of two Se atoms induced by rippling, which is then converted to three-dimensional (3D) ripple distortions. The dynamics of 3D ripple deformation can thus be directly visualized at the atomic scale by sequential STEM imaging. In addition, the reconstructed images provide the first opportunity for directly testing the validity of the classical theory of thermal fluctuations. Our method paves the way for a 3D reconstruction of a dynamical process in two-dimensional materials with a reasonable temporal resolution.
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Transition metal dichalcogenide heterostructures provide a versatile platform to explore electronic and excitonic phases. As the excitation density exceeds the critical Mott density, interlayer excitons are ionized into an electron-hole plasma phase. The transport of the highly non-equilibrium plasma is relevant for high-power optoelectronic devices but has not been carefully investigated previously. Here, we employ spatially resolved pump-probe microscopy to investigate the spatial-temporal dynamics of interlayer excitons and hot-plasma phase in a MoSe2/WSe2 twisted bilayer. At the excitation density of â¼1014 cm-2, well exceeding the Mott density, we find a surprisingly rapid initial expansion of hot plasma to a few microns away from the excitation source within â¼0.2 ps. Microscopic theory reveals that this rapid expansion is mainly driven by Fermi pressure and Coulomb repulsion, while the hot carrier effect has only a minor effect in the plasma phase.
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Excitons, electron-hole pairs in semiconductors, can be utilized as information carriers with a spin or valley degree of freedom. However, manipulation of excitons' motion is challenging because of their charge-neutral characteristic and short recombination lifetimes. Here we demonstrate electric-field-driven drift and funneling of charged excitons (i.e., trions) toward the center of a MoSe2 monolayer. Using a simple bottom-gate device, we control the electric fields in the vicinity of the suspended monolayer, which increases the trion density and pulls down the layer. We observe that locally excited trions are subjected to electric force and, consequently, drift toward the center of the stretched layer. The exerting electric force on the trion is estimated to be 102-104 times stronger than the strain-induced force in the stretched monolayer, leading to the successful observation of trion drift under continuous-wave excitation. Our findings provide a new route for manipulating trions and achieving new types of optoelectronic devices.
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We report the synthesis of ethylenediamine-intercalated NbSe2 and Li-ethylenediamine-intercalated MoSe2 single crystals with increased interlayer distances and their electronic structures measured by means of angle-resolved photoemission spectroscopy (ARPES). X-ray diffraction patterns and transmission electron microscopy images confirm the successful intercalation and an increase in the interlayer distance. ARPES measurement reveals that intercalated NbSe2 shows an electronic structure almost identical to that of monolayer NbSe2. Intercalated MoSe2 also returns the characteristic feature of the monolayer electronic structure, a direct band gap, which generates sizable photoluminescence even in the bulk form. Our results demonstrate that the properties and phenomena of the monolayer transition metal dichalcogenides can be achieved with large-scale bulk samples by blocking the interlayer interaction through intercalation.
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Artificially engineered 2D materials offer unique physical properties for thermal management, surpassing naturally occurring materials. Here, using van der Waals epitaxy, we demonstrate the ability to engineer extremely insulating thermal metamaterials based on atomically thin lattice-mismatched Bi2Se3/MoSe2 superlattices and graphene/PdSe2 heterostructures with exceptional thermal resistances (70-202 m2 K/GW) and ultralow cross-plane thermal conductivities (0.012-0.07 W/mK) at room temperature, comparable to those of amorphous materials. Experimental data obtained using frequency-domain thermoreflectance and low-frequency Raman spectroscopy, supported by tight-binding phonon calculations, reveal the impact of lattice mismatch, phonon-interface scattering, size effects, temperature, and interface thermal resistance on cross-plane heat dissipation, uncovering different thermal transport regimes and the dominant role of long-wavelength phonons. Our findings provide essential insights into emerging synthesis and thermal characterization methods and valuable guidance for the development of large-area heteroepitaxial van der Waals films of dissimilar materials with tailored thermal transport characteristics.
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Vertical van der Waals heterostructures of semiconducting transition metal dichalcogenides realize moiré systems with rich correlated electron phases and moiré exciton phenomena. For material combinations with small lattice mismatch and twist angles as in MoSe2-WSe2, however, lattice reconstruction eliminates the canonical moiré pattern and instead gives rise to arrays of periodically reconstructed nanoscale domains and mesoscopically extended areas of one atomic registry. Here, we elucidate the role of atomic reconstruction in MoSe2-WSe2 heterostructures synthesized by chemical vapor deposition. With complementary imaging down to the atomic scale, simulations, and optical spectroscopy methods, we identify the coexistence of moiré-type cores and extended moiré-free regions in heterostacks with parallel and antiparallel alignment. Our work highlights the potential of chemical vapor deposition for applications requiring laterally extended heterosystems of one atomic registry or exciton-confining heterostack arrays.