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The formation of a heterostructure with plasmonic nanoparticles drastically alters the optoelectronic properties of graphene quantum dots (GQDs), resulting in exceptional properties. In the present work, we prepare nitrogen-doped GQDs decorated on gold nanoparticles (Au@N-GQDs) by a one-step green reduction method and study its extraordinary fluorescence and photoresponse characteristics. The as-prepared Au@N-GQDs show more than one order of magnitude enhancement in the fluorescence intensity as compared to the bare N-GQDs, which is attributed to hot electron generation and improved absorption in N-GQDs by local field enhancement and the modification of the edge functional groups. Because of the selective coordination to Fe 3+ ions, the Au@N-GQDs exhibit extraordinary quenching of fluorescence, with ultrahigh sensitivity for the detection of Fe 3+ (<1 nM). A new model for the charge-transfer dynamics is developed involving the Langmuir's law of adsorption to explain the unusual quenching, which strongly deviates from the known models of static/dynamic quenching. The proposed sensor is successfully implemented for the ultrasensitive detection of Fe 3+ ions in human serum and Brahmaputra river water samples, representing its high potential applications in clinical as well as environmental diagnosis. Additionally, because of its high absorption in the UV−vis−NIR region and high charge density with long life excitons, the Au@N-GQDs are utilized as photodetectors with ∼10 4 times faster response than that of bare N-GQDs.

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We have examined the electronic structure evolution in transition metal dichalcogenides MX2 where M = Mo, W and X = S, Se, and Te. These are generally referred to as van der Waals materials on the one hand, yet one has band gap changes as large as 0.6 eV with thickness in some instances. This does not seem to be consistent with a description where the dominant interactions are van der Waals interactions. Mapping onto a tight binding model allows us to quantify the electronic structure changes, which are found to be dictated solely by interlayer hopping interactions. Different environments that an atom encounters could change the Madelung potential and therefore the onsite energies. This could happen while going from the monolayer to the bilayer as well as in cases where the stackings are different from what is found in 2H structures. These effects are quantitatively found to be negligible, enabling us to quantify the thickness-dependent electronic structure changes as arising from interlayer interactions alone.