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Register a new userUnsaturated Single Atoms on Monolayer Transition Metal Dichalcogenides for Ultrafast Hydrogen Evolution
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Large scale implementation of electrochemical water splitting for hydrogen evolution requires cheap and efficient catalysts to replace expensive platinum. Molybdenum disulfide is one of the most promising alternative catalysts but its intrinsic activity is still inferior to platinum. There is therefore a need to explore new active site origins in molybdenum disulfide with ultrafast reaction kinetics and to understand their mechanisms. Here, we report a universal cold hydrogen plasma reduction method for synthesizing different single atoms sitting on two-dimensional monolayers. In case of molybdenum disulfide, we design and identify a new type of active site, i.e., unsaturated Mo single atoms on cogenetic monolayer molybdenum disulfide. The catalyst shows exceptional intrinsic activity with a Tafel slope of 35.1 mV dec-1 and a turnover frequency of ~10^3 s-1 at 100 mV, based on single flake microcell measurements. Theoretical studies indicate that coordinately unsaturated Mo single atoms sitting on molybdenum disulfide increase the bond strength between adsorbed hydrogen atoms and the substrates through hybridization, leading to fast hydrogen adsorption/desorption kinetics and superior hydrogen evolution activity. This work shines fresh light on preparing highly-efficient electrocatalysts for water splitting and other electrochemical processes, as well as provides a general method to synthesize single atoms on two-dimensional monolayers.
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To advance fundamental understanding, and ultimate application, of transition-metal dichalcogenide (TMD) monolayers, it is essential to develop capabilities for the synthesis of high-quality single-layer samples. Molecular beam epitaxy (MBE), a leading technique for the fabrication of the highest-quality epitaxial films of conventional semiconductors has, however, typically yielded only small grain sizes and sub-optimal morphologies when applied to the van der Waals growth of monolayer TMDs. Here, we present a systematic study on the influence of adatom mobility, growth rate, and metal:chalcogen flux on the growth of NbSe2, VSe2 and TiSe2 using MBE. Through this, we identify the key drivers and influence of the adatom kinetics that control the epitaxial growth of TMDs, realising four distinct morphologies of the as-grown compounds. We use this to determine optimised growth conditions for the fabrication of high-quality monolayers, ultimately realising the largest grain sizes of monolayer TMDs that have been achieved to date via MBE growth.
The optical properties of atomically thin transition metal dichalcogenide (TMDC) semiconductors are shaped by the emergence of correlated many-body complexes due to strong Coulomb interaction. Exceptional electron-hole exchange predestines TMDCs to study fundamental and applied properties of Coulomb complexes such as valley depolarization of excitons and fine-structure splitting of trions. Biexcitons in these materials are less understood and it has been established only recently that they are spectrally located between exciton and trion. Here we show that biexcitons in monolayer TMDCs exhibit a distinct fine structure on the order of meV due to electron-hole exchange. Ultrafast pump-probe experiments on monolayer WSe$_2$ reveal decisive biexciton signatures and a fine structure in excellent agreement with a microscopic theory. We provide a pathway to access biexciton spectra with unprecedented accuracy, which is valuable beyond the class of TMDCs, and to understand even higher Coulomb complexes under the influence of electron-hole exchange.
Recently, the celebrated Keldysh potential has been widely used to describe the Coulomb interaction of few-body complexes in monolayer transition-metal dichalcogenides. Using this potential to model charged excitons (trions), one finds a strong dependence of the binding energy on whether the monolayer is suspended in air, supported on SiO$_2$, or encapsulated in hexagonal boron-nitride. However, empirical values of the trion binding energies show weak dependence on the monolayer configuration. This deficiency indicates that the description of the Coulomb potential is still lacking in this important class of materials. We address this problem and derive a new potential form, which takes into account the three atomic sheets that compose a monolayer of transition-metal dichalcogenides. The new potential self-consistently supports (i) the non-hydrogenic Rydberg series of neutral excitons, and (ii) the weak dependence of the trion binding energy on the environment. Furthermore, we identify an important trion-lattice coupling due to the phonon cloud in the vicinity of charged complexes. Neutral excitons, on the other hand, have weaker coupling to the lattice due to the confluence of their charge neutrality and small Bohr radius.
Many-body interactions in monolayer transition-metal dichalcogenides are strongly affected by their unique band structure. We study these interactions by measuring the energy shift of neutral excitons (bound electron-hole pairs) in gated WSe$_2$ and MoSe$_2$. Surprisingly, while the blueshift of the neutral exciton, $X^0$, in electron-doped samples can be more than 10~meV, the blueshift in hole-doped samples is nearly absent. Taking into account dynamical screening and local-field effects, we present a transparent and analytical model that elucidates the crucial role played by intervalley plasmons in electron-doped conditions. The energy shift of $X^0$ as a function of charge density is computed showing agreement with experiment, where the renormalization of $X^0$ by intervalley plasmons yields a stronger blueshift in MoSe$_2$ than in WSe$_2$ due to differences in their band ordering.
Just as photons are the quanta of light, plasmons are the quanta of orchestrated charge-density oscillations in conducting media. Plasmon phenomena in normal metals, superconductors and doped semiconductors are often driven by long-wavelength Coulomb interactions. However, in crystals whose Fermi surface is comprised of disconnected pockets in the Brillouin zone, collective electron excitations can also attain a shortwave component when electrons transition between these pockets. Here, we show that the band structure of monolayer transition-metal dichalcogenides gives rise to an intriguing mechanism through which shortwave plasmons are paired up with excitons. The coupling elucidates the origin for the optical side band that is observed repeatedly in monolayers of WSe$_2$ and WS$_2$ but not understood. The theory makes it clear why exciton-plasmon coupling has the right conditions to manifest itself distinctly only in the optical spectra of electron-doped tungsten-based monolayers.
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