Transition Metal Dichalcogenides Crystals Research Articles

Identification of triangular single crystals of transition metal dichalcogenides based on the detection algorithm.

The distinctive properties and facile integration of 2D materials hold the potential to offer promising avenues for the on-chip photonic devices, and the expeditious and nondestructive identification and localization of diverse fundamental building blocks become key prerequisites. Here, we present a methodology grounded in digital image processing and deep learning, which effectively achieves the detection and precise localization of four monolayer-thick triangular single crystals of transition metal dichalcogenides with the mean average precision above 90%, and the approach demonstrates robust recognition capabilities across varied imaging conditions encompassing both white light and monochromatic light. This stands poised to serve as a potent data-driven tool enhancing the characterizing efficiency and holds the potential to expedite research initiatives and applications founded on the utilization of 2D materials.

Selective oxidation of metallic contacts for localized chemical vapor deposition growth of 2D-transition metal dichalcogenides

Chemical vapor deposition (CVD) is the most common fabrication method for transition metal dichalcogenides (TMDs) where direct chemical vapor phase reaction between an oxide transition metal and chalcogen powder results in formation of high-quality crystals of TMDs. However, in this method the nucleation is often random with incomplete nucleation and non-uniform thickness. In this work we studied the formation of a localized transition metal oxide which resulted in controllable growth of mono- to few-layer MoS2 around the formed oxide region. Bulk molybdenum patterns were irradiated with a 532 nm continuous wave laser creating a localized hot-spot which, under ambient conditions, resulted in the formation of molybdenum oxide. The characteristics of the subsequent MoS2 growth depended on the type and thickness of the MoOx which was determined by the power and duration of laser exposure. The resulting MoOx and MoS2 growth around the localized oxide regions were investigated by Raman and photoluminescence spectroscopy. Our studies have shown that exposing bulk molybdenum patterns to 10 mW of laser power for about 2s results in the minimal formation of MoO2 which coincides with high quality mono- to few-layer MoS2 growth.

Optical grade transformation of monolayer transition metal dichalcogenides via encapsulation annealing.

Monolayer transition metal dichalcogenides (TMDs) have emerged as highly promising candidates for optoelectronic applications due to their direct band gap and strong light-matter interactions. However, exfoliated TMDs have demonstrated optical characteristics that fall short of expectations, primarily because of significant defects and associated doping in the synthesized TMD crystals. Here, we report the improvement of optical properties in monolayer TMDs of MoS2, MoSe2, WS2, and WSe2, by hBN-encapsulation annealing. Monolayer WSe2 showed 2000% enhanced photoluminescence quantum yield (PLQY) and 1000% increased lifetime after encapsulation annealing at 1000 °C, which are attributed to dominant radiative recombination of excitons through dedoping of monolayer TMDs. Furthermore, after encapsulation annealing, the transport characteristics of monolayer WS2 changed from n-type to ambipolar, along with an enhanced hole transport, which also support dedoping of annealed TMDs. This work provides an innovative approach to elevate the optical grade of monolayer TMDs, enabling the fabrication of high-performance optoelectronic devices.

Observation of Sub-10 nm Transition Metal Dichalcogenide Nanocrystals in Rapidly Heated van der Waals Heterostructures.

Two-dimensional materials, such as transition metal dichalcogenides (TMDCs), have the potential to revolutionize the field of electronics and photonics due to their unique physical and structural properties. This research presents a novel method for synthesizing crystalline TMDCs crystals with <10 nm size using ultrafast migration of vacancies at elevated temperatures. Through in situ and ex situ processing and using atomic-level characterization techniques, we analyzed the shape, size, crystallinity, composition, and strain distribution of these nanocrystals. These nanocrystals exhibit electronic structure signatures that differ from the 2D bulk: i.e., uniform mono- and multilayers. Further, our in situ, vacuum-based synthesis technique allows observation and comparison of defect and phase evolution in these crystals formed under van der Waals heterostructure confinement versus unconfined conditions. Overall, this research demonstrates a solid-state route to synthesizing uniform nanocrystals of TMDCs and lays the foundation for materials science in confined 2D spaces under extreme conditions.

(Invited) Molecular Reaction Imaging of Charge Transport in MoS2 Nanoflake Photoelectrodes

Transition metal dichalcogenides (TMD) such as WSe2 and MoS2 are highly efficient and stable light absorbers in TMD∣I−,I3 −∣Pt liquid junction solar cells. It is generally accepted that TMD crystals with a large fraction of exposed edge sites exhibit lower power conversion efficiencies (PCEs) than apparently smooth crystals. However, one open question is why does the PCE vary significantly from one crystal to another? Answering this critical question could lead to robust syntheses for high quality and uniform TMD samples. In this work, we apply nanoscale photoelectrochemical microscopy techniques to study n-type TMD nano flake∣I−,I3 −∣Pt cells. Using a combination of near-diffraction-limited photocurrent mapping and molecular reaction imaging techniques, we reveal a previously hidden surface recombination process: photogenerated holes in hidden p-type domains travel micron-scale distances parallel to the solid/liquid interface and preferentially react with iodide at step-edges. The overall efficiency of the nanoflake, as evidenced from whole nanoflake-level photoelectrochemical measurements, is dictated by the size, efficiency, and location of n- and p-type domains. These results provide a unifying view of efficiency losses in smooth TMD photoelectrodes and open the possibility to design electrode architectures that leverage the long-range lateral charge transport property for photoelectrocatalysis.

Unravelling the Data Retention Mechanisms under Thermal Stress on 2D Memristors.

Memristors based on two-dimensional (2D) materials are a rapidly growing research area due to their potential in energy-efficient in-memory processing and neuromorphic computing. However, the data retention of these emerging memristors remains sparsely investigated, despite its crucial importance to device performance and reliability. In this study, we employ kinetic Monte-Carlo simulations to investigate the data retention of a 2D planar memristor. The operation of the memristor depends on field-driven on defect migration, while thermal diffusion gradually evens the defect distribution, leading to the degradation of the high resistance state (HRS) and diminishing the ON/OFF ratio. Notably, we examine the resilience of devices based on single crystals of transition metal dichalcogenides (TMDs) in harsh environments. Specifically, our simulations show that MoS2-based devices have negligible degradation after 10 years of thermal annealing at 400 K. Furthermore, the variability in data retention lifetime across different temperatures is less than 22%, indicating a relatively consistent performance over a range of thermal conditions. We also demonstrate that device miniaturization does not compromise data retention lifetime. Moreover, employing materials with higher activation energy for defect migration can significantly enhance data retention at the cost of increased switching voltage. These findings shed light on the behavior of 2D memristors and pave the way for their optimization in practical applications.

Valley-dependent vortex emission from exciton-polariton in non-centrosymmetric transition metal dichalcogenide metasurfaces.

Transition metal dichalcogenides (TMDs) have attracted great attention in valleytronics. Owing to the giant valley coherence at room temperature, valley pseudospin of TMDs open a new degree of freedom to encode and process binary information. The valley pseudospin only exists in non-centrosymmetric TMDs (e.g., monolayer or 3R-stacked multilayer), which is prohibited in conventional centrosymmetric 2H-stacked crystals. Here, we propose a general recipe to generate valley-dependent vortex beams by using a mix-dimensional TMD metasurface composed of nanostructured 2H-stacked TMD crystals and monolayer TMDs. Such an ultrathin TMD metasurface involves a momentum-space polarization vortex around bound states in the continuum (BICs), which can simultaneously achieve strong coupling (i.e., form exciton polaritons) and valley-locked vortex emission. Moreover, we report that a full 3R-stacked TMD metasurface can also reveal the strong-coupling regime with an anti-crossing pattern and a Rabi splitting of 95 meV. The Rabi splitting can be precisely controlled by geometrically shaping the TMD metasurface. Our results provide an ultra-compact TMD platform for controlling and structuring valley exciton polariton, in which the valley information is linked with the topological charge of vortex emission, which may advance valleytronic, polaritonic, and optoelectronic applications.

Direct CVD Synthesis of MoS2 Monolayers on Glass by Carbothermal Reduction

Chemical vapor deposition (CVD) synthesis for two-dimensional (2D) transition-metal dichalcogenides (TMDCs) is fundamentally important for realizing high-quality single crystals of TMDCs for future electronic and optoelectronic device applications. However, CVD synthesis of TMDCs generally requires a high synthetic temperature (>700 °C), which limits the choice of growth substrates and their broad applications. In this work, we present direct CVD synthesis of 2D MoS2 on glass. The CVD growth temperature was significantly decreased to 500 °C by employing carbothermal reduction, which uses carbon as the catalyst for reducing the thermal decomposition temperature of MoO3 precursors. MoS2 single crystals grown on glass showed no observable degradation in electrical, optical, and structural properties compared to MoS2 grown at high temperatures. The MoS2 grown on glass exhibited field effect mobility around 7.6 cm2 V–1 s–1 and a high ON/OFF ratio of up to 107, photoresponsivity up to 40 A/W, and stable and repeatable photocurrent. These findings demonstrate a promising strategy in the CVD growth of 2D materials and the design of their flexible and transparent devices.

Transition metal dichalcogenide nanospheres for high-refractive-index nanophotonics and biomedical theranostics

Recent developments in the area of resonant dielectric nanostructures have created attractive opportunities for concentrating and manipulating light at the nanoscale and the establishment of the new exciting field of all-dielectric nanophotonics. Transition metal dichalcogenides (TMDCs) with nanopatterned surfaces are especially promising for these tasks. Still, the fabrication of these structures requires sophisticated lithographic processes, drastically complicating application prospects. To bridge this gap and broaden the application scope of TMDC nanomaterials, we report here femtosecond laser-ablative fabrication of water-dispersed spherical TMDC (MoS2 and WS2) nanoparticles (NPs) of variable size (5 to 250 nm). Such NPs demonstrate exciting optical and electronic properties inherited from TMDC crystals, due to preserved crystalline structure, which offers a unique combination of pronounced excitonic response and high refractive index value, making possible a strong concentration of electromagnetic field in the NPs. Furthermore, such NPs offer additional tunability due to hybridization between the Mie and excitonic resonances. Such properties bring to life a number of nontrivial effects, including enhanced photoabsorption and photothermal conversion. As an illustration, we demonstrate that the NPs exhibit a very strong photothermal response, much exceeding that of conventional dielectric nanoresonators based on Si. Being in a mobile colloidal state and exhibiting superior optical properties compared to other dielectric resonant structures, the synthesized TMDC NPs offer opportunities for the development of next-generation nanophotonic and nanotheranostic platforms, including photothermal therapy and multimodal bioimaging.

Molecular Reaction Imaging of a Surface Recombination Process Explains Performance Variation Among Smooth MoS2 Photoelectrodes

Transition metal dichalcogenides (TMD) such as WSe2 and MoS2 are highly efficient and stable light absorbers in TMD∣I−,I3 −∣Pt liquid junction solar cells. It is generally accepted that TMD crystals with a large fraction of exposed edge sites exhibit lower power conversion efficiencies (PCEs) than apparently smooth crystals. However, one open question is why does the PCE vary significantly from one crystal to another? Answering this critical question could lead to robust syntheses for high quality and uniform TMD samples. In this work, we apply nanoscale photoelectrochemical microscopy techniques to study n-type TMD nanoflake∣I−,I3 −∣Pt cells. Using a combination of near-diffraction-limited photocurrent mapping and molecular reaction imaging techniques, we reveal a previously hidden surface recombination process: photogenerated holes in hidden p-type domains travel micron-scale distances parallel to the solid/liquid interface and preferentially react with iodide at step-edges. The overall efficiency of the nanoflake, as evidenced from whole nanoflake-level photoelectrochemical measurements, is dictated by the size, efficiency, and location of n- and p-type domains. These results provide a unifying view of efficiency losses in smooth TMD photoelectrodes and open the possibility to design electrode architectures that leverage the long-range lateral charge transport property for photoelectrocatalysis.

Fabrication of high-quality PMMA/SiOx spaced planar microcavities for strong coupling of light with monolayer WS2 excitons

Exciton polaritons in atomically thin transition metal dichalcogenide crystals (monolayer TMDCs) have emerged as a promising candidate to enable topological transport, ultra-efficient laser technologies, and collective quantum phenomena such as polariton condensation and superfluidity at room temperature. However, integrating monolayer TMDCs into high-quality planar microcavities to achieve the required strong coupling between the cavity photons and the TMDC excitons (bound electron–hole pairs) has proven challenging. Previous approaches to integration had to compromise between various adverse effects on the strength of light–matter interactions in the monolayer, the cavity photon lifetime, and the lateral size of the microcavity. Here, we demonstrate a scalable approach to fabricate high-quality planar microcavities with an integrated monolayer WS2 layer-by-layer by using polymethyl methacrylate/silicon oxide (PMMA/SiOx) as a cavity spacer. Because the exciton oscillator strength is well protected against the required processing steps by the PMMA layer, the microcavities investigated in this work, which have quality factors of above 103, can operate in the strong light–matter coupling regime at room temperature. This is an important step toward fabricating wafer-scale and patterned microcavities for engineering the exciton-polariton potential landscape, which is essential for enabling many proposed technologies.

Towards compact phase-matched and waveguided nonlinear optics in atomically layered semiconductors

Nonlinear frequency conversion provides essential tools for light generation, photon entanglement, and manipulation. Transition metal dichalcogenides (TMDs) possess huge nonlinear susceptibilities and 3R-stacked TMD crystals further combine broken inversion symmetry and aligned layering, representing ideal candidates to boost the nonlinear optical gain with minimal footprint. Here, we report on the efficient frequency conversion of 3R-MoS2, revealing the evolution of its exceptional second-order nonlinear processes along the ordinary (in-plane) and extraordinary (out-of-plane) directions. By measuring second harmonic generation (SHG) of 3R-MoS2 with various thickness - from monolayer (~0.65 nm) to bulk (~1 {\mu}m) - we present the first measurement of the in-plane SHG coherence length (~530 nm) at 1520 nm and achieve record nonlinear optical enhancement from a van der Waals material, >10^4 stronger than a monolayer. It is found that 3R-MoS2 slabs exhibit similar conversion efficiencies of lithium niobate, but within propagation lengths >100-fold shorter at telecom wavelengths. Furthermore, along the extraordinary axis, we achieve broadly tunable SHG from 3R-MoS2 in a waveguide geometry, revealing the coherence length in such structure for the first time. We characterize the full refractive index spectrum and quantify both birefringence components in anisotropic 3R-MoS2 crystals with near-field nano-imaging. Empowered with these data we assess the intrinsic limits of the conversion efficiency and nonlinear optical processes in 3R-MoS2 attainable in waveguide geometries. Our analysis highlights the potential of 3R-stacked TMDs for integrated photonics, providing critical parameters for designing highly efficient on-chip nonlinear optical devices including periodically poled structures, resonators, compact optical parametric oscillators and amplifiers, and optical quantum circuits.

Salt-Assisted 2H-to-1T' Phase Transformation of Transition Metal Dichalcogenides.

Phase engineering of nanomaterials (PEN) has demonstrated great potential in the fields of catalysis, electronics, energy storage and conversion, and condensed matter physics. Recently, transition metal dichalcogenides (TMDs) with unconventional metastable phases (e.g., 1T and 1T') have attracted increasing research interest due to their unique and appealing physicochemical properties. However, there is still a lack of a simple, universal, and controlled method for the preparation of large-scale and high-purity unconventional-phase TMD crystals, restricting their further fundamental study and practical applications. Here, a facile, one-step salt-assisted general strategy is reported for the controlled phase transformation of commercially available TMDs with conventional 2H phase, yielding a large amount of metastable 1T'-phase TMDs, including WS2 , WSe2 , MoS2 , and MoSe2 . It is found that the easily accessible metal salts, such as K2 C2 O4 ·H2 O, K2 CO3 , Na2 CO3 , Rb2 CO3 , Cs2 CO3 , KHCO3 , NaHCO3 , and NaC2 O4 , can be used to assist the 2H-to-1T' phase transformation, greatly simplifying the synthetic process for producing metastable 1T'-TMDs. Importantly, this method can also be used to prepare 1T'-TMD alloys, such as 1T'-WS2 x Se2(1- x ) . This newly developed strategy is robust and highly effective, which can also be used for the phase engineering of other materials with various polymorphs.

Self-Expanding Molten Salt-Driven Growth of Patterned Transition-Metal Dichalcogenide Crystals.

Transition-metal dichalcogenides (TMDs) have been considered potential materials for the next generation of semiconductors. Realizing controllable growth of TMD crystals is a prerequisite for their future applications, which remains challenging. Here, we reveal a new mechanism of self-expanding molten salt-driven growth for a salt-assisted method and achieve the patterned growth of TMD single-crystal arrays with a size of hundreds of micrometers. Time-of-flight secondary ion mass spectroscopy and other spectroscopy characterizations identify the component of the molten salt solution. Microscopic characterizations reveal the existence of salt solution as an interlayer between a TMD monolayer and the silicon substrate as well as particles along the crystal edge. The edged salt solution serves as a self-expanding liquid substrate, which confines the reactive sites to the localized liquid surface, thus avoiding random nucleation. The surface reaction also assures monolayer crystal formation due to self-limiting growth. Besides, the liquid substrate affords sources and spreads itself continuously owing to the nonwetting effect on TMD crystals, thereby facilitating the continuous extension of the TMD monolayer. This work provides novel insights into the controllable synthesis of TMD monolayers and paves the way for the fabrication of TMD-based integrated functional devices.

Theoretical understanding of electronic and mechanical properties of 1T' transition metal dichalcogenide crystals.

Transition metal dichalcogenides (TMDs) with a 1T′ layer structure have recently received intense interest due to their outstanding physical and chemical properties. While the physicochemical behaviors of 1T′ TMD monolayers have been widely investigated, the corresponding properties of layered 1T′ TMD crystals have rarely been studied. As TMD monolayers do not have interlayer interactions, their physicochemical properties will differ from those of layered TMD materials. In this study, the electronic and mechanical characteristics of a range of 1T′ TMDs are systematically examined by means of density functional theory (DFT) calculations. Our results reveal that the properties of 1T′ TMDs are mainly affected by their anions. The disulfides are stiffer and more rigid, diselenides are more brittle. In addition, the 1T′ polytype is softer than 2H TMDs. Comparison with the properties of the monolayers shows that the interlayer van der Waals forces can slightly weaken the TM–X covalent bonding strength, which can further influence the mechanical properties. These insights revealed by our theoretical studies may boost more applications of 1T′ TMD materials.

Facile fabrication of 2D material multilayers and vdW heterostructures with multimodal microscopy and AFM characterization

Reliable transfer processes that enable manipulation of two-dimensional (2D) materials, e.g., transition metal dichalcogenides (TMDCs) and MXenes, from one substrate to another has been a necessity for successful device fabrication. With both mechanical exfoliation and chemical vapor deposition (CVD) widely used, a versatile, clean, deterministic, and yet simple transfer technique is highly needed. To address such need, we developed a transfer method that takes advantage of wettability contrast between interfaces without the use of sacrificial layers or chemical processes. More importantly, a setup was developed to carry out this transfer method with high sample selectivity and fine control of the position and orientation of transferred TMDC crystals, a feature required for fabrication of the devices based on vertical 2D heterostructures. Using both exfoliated and CVD grown materials and subsequent atomic force microscopy (AFM), photoluminescence (PL), confocal Raman and tip enhanced Raman spectroscopy (TERS) characterization, we ascertained the quality of interfaces resulting from the transfer process while preserving excellent 2D material integrity. PL and TERS maps revealed nanometer-scale heterogeneities in the interfaces of fabricated heterostructures, which should enable further perfection of the transfer technique. TERS/TEPL information were employed to identify areas suitable for nanodevice fabrication, making the reported transfer and characterization methods ideal for making high quality assembly of 2D heterostructure more accessible, which should facilitate exploration of vertical 2D heterostructures for applications in electronics, batteries, solar cells, and twistronics.

Strengthening and Weakening by Dislocations in Monolayer MoS2

Dislocations govern the properties of crystals. Yet, how pentagon–heptagon (5|7) pairs in grain boundaries (GBs) affect the mechanical properties of MoS2 remains poorly known. Using atomistic simulations and the continuum disclination dipole model, we show that depending on the tilt angle and 5|7 dislocation arrangement, MoS2 GB strength can be enhanced or reduced with the tilt angle. For zigzag-tilt GBs primarily composed of Mo5|7 + S5|7 dislocations, GB strength monotonically increases as the square of the tilt angle. For armchair-tilt GBs with Mo5|7 or S5|7 dislocations, however, the trend of GB strength breaks down, as dislocations are unevenly spaced. Moreover, mechanical failure initiates at the bond shared by 5|7 rings, in contrast to graphene in which failure occurs at the bond shared by 6|7 rings. This work provides new insights into the mechanical design of synthetic transition metal dichalcogenide crystals via dislocation engineering.

Motional narrowing, ballistic transport, and trapping of room-temperature exciton polaritons in an atomically-thin semiconductor

Monolayer transition metal dichalcogenide crystals (TMDCs) hold great promise for semiconductor optoelectronics because their bound electron-hole pairs (excitons) are stable at room temperature and interact strongly with light. When TMDCs are embedded in an optical microcavity, excitons can hybridise with cavity photons to form exciton polaritons, which inherit useful properties from their constituents. The ability to manipulate and trap polaritons on a microchip is critical for applications. Here, we create a non-trivial potential landscape for polaritons in monolayer WS2, and demonstrate their trapping and ballistic propagation across tens of micrometers. We show that the effects of dielectric disorder, which restrict the diffusion of WS2 excitons and broaden their spectral resonance, are dramatically reduced for polaritons, leading to motional narrowing and preserved partial coherence. Linewidth narrowing and coherence are further enhanced in the trap. Our results demonstrate the possibility of long-range dissipationless transport and efficient trapping of TMDC polaritons in ambient conditions.

Signature of Spin-Resolved Quantum Point Contact in p-Type Trilayer WSe2 van der Waals Heterostructure.

In this study, an electrostatically induced quantum confinement structure, so-called quantum point contact, has been realized in a p-type trilayer tungsten diselenide-based van der Waals heterostructure with modified van der Waals contact method with degenerately doped transition metal dichalcogenide crystals. Clear quantized conductance and pinch-off state through the one-dimensional confinement were observed by dual-gating of split gate electrodes and top gate. Conductance plateaus were observed at a step of e2/h in addition to quarter plateaus such as 0.25 × 2e2/h at a finite bias voltage condition indicating the signature of intrinsic spin-polarized quantum point contact.

Synthesis of Large-Area MoSe2 Monolayer Film for Surface-Enhanced Raman Scattering Analysis

Ultrathin two-dimensional transition metal dichalcogenides represent a promising new class of materials with surface-enhanced Raman scattering (SERS) activities. Previous work mainly focused on the SERS effects of transition metal dichalcogenide crystals with sizes of micrometer scale. The enhancement effect is usually nonuniform on the SERS substrates. In this paper, we report a chemical vapor deposition method for the preparation of centimeter-scale MoSe2 films with uniform and high SERS activity. The molybdenum precursors are supplied in a “face-to-face” manner from a silica gel plate to the growth substrate, which guarantees uniform nucleation and growth of the monolayer MoSe2. We demonstrate that the monolayer MoSe2 film has strong SERS effect, which can be attributed to charge transfer between MoSe2 and the probe molecules. The detection limit of Rhodamine B on monolayer MoSe2 is determined to be 10[Formula: see text][Formula: see text]mol/L, and the Raman enhancement factor is estimated to be [Formula: see text]. Due to its atomic uniformity and chemical stability, the MoSe2 film can serve as an ideal two-dimensional SERS material for detection of various molecules.