Graphene-hBN non-van der Waals vertical heterostructures for four- electron oxygen reduction reaction.

A novel vertical non-van der Waals (non-vdW) heterostructure of graphene and hexagonal boron nitride (G/hBN) is realized and its application in direct four-electron oxygen reduction reaction (ORR) in alkaline medium is established. The G/hBN differs from previously demonstrated vdW heterostructures, where it has a chemical bridging between graphene and hBN allowing a direct charge transfer - resulting in high ORR activity. The ORR efficacy of G/hBN is compared with that of graphene-hBN vdW structure and individual layers of graphene and hBN along with that of benchmark platinum/carbon (Pt/C). The ORR activity of G/hBN is found to be on par with Pt/C in terms of current density but with much higher electrochemical stability and methanol tolerance. The onset potential of the G/hBN is found to be improved from 780 mV at a glassy carbon electrode to 930 mV and 940 mV in gold and platinum electrodes, respectively, indicating its substrate-dependent catalytic activity. This opens possibilities of new benchmark catalysts of metals capped with G/hBN atomic layers, where the underneath metal is protected while keeping the activity similar to that of pristine metal. Density functional theory-based calculations are found to be supporting the observed augmented ORR performance of G/hBN.

On the electronic and spin-valley coupling of vanadium doped MoS2(1-x)Se2xmonolayers.

Monolayers of MoS2with tunable bandgap and valley positions are highly demanding for their applications in opto-spintronics. Herein, selenium (Se) and vanadium (V) co-doped MoS2monolayers (vanadium doped MoS2(1-x)Se2x(V-MoSSe)) are developed and showed their variations in the electronic and optical properties with dopant content. Vanadium gets substitutionally (in place of Mo) doped within the MoS2lattice while selenium doped in place of sulfur, as shown by a detailed microstructure and spectroscopy analyses. The bandgap tunability with selenium doping can be achieved while valley shift is occurred due to the doping of vanadium. Chemical vapor deposition assisted grown MoS2(also selenium doped MoS2as shown here) is known for its n-type transport behavior while vanadium doping is found to be changing its nature to p-doping. Chirality dependent photoexcitation studies indicate a room temperature valley splitting in V-MoSSe (∼8 meV), where such a valley splitting is verified using density functional theory based calculations.

Role of processing parameters in CVD grown crystalline monolayer MoSe2.

The quality of as-synthesized monolayers plays a significant role in atomically thin semiconducting transition metal dichalcogenides (TMDCs) to determine the electronic and optical properties. For designing optoelectronic devices, exploring the effect of processing parameters on optical properties is a prerequisite. In this view, we present the influence of processing parameters on the lattice and quasiparticle dynamics of monolayer MoSe2. The lab-built chemical vapour deposition (CVD) setup is used to synthesize monolayer MoSe2 flakes with varying shapes, including sharp triangle (ST), truncated triangle (TT), hexagon, and rough edge circle (REC). In particular, the features of as-synthesized monolayer MoSe2 flakes are examined using Raman and photoluminescence (PL) spectroscopy. Raman spectra reveal that the frequency difference between the A1g and E1 2g peaks is >45 cm-1 in all the monolayer samples. PL spectroscopy also shows that the synthesized MoSe2 flakes are monolayer in nature with a direct band gap in the range of 1.50-1.58 eV. Furthermore, the variation in the direct band gap is analyzed using the spectral weight of quasiparticles in PL emission, where the intensity ratio {I(A0)/I(A-)} and trion binding energy are found to be ∼1.1-5.0 and ∼23.1-47.5 meV in different monolayer MoSe2 samples. Hence, these observations manifest that the processing parameters make a substantial contribution in tuning the vibrational and excitonic properties.