As opposed to inorganic counterparts, organic quantum dots often exhibit lower fluorescence efficiencies and are complex to synthesize. Here we develop nitrogen‐doped (N‐GQDs) and nitrogen–sulfur codoped (NS‐GQDs) graphene quantum dots exhibiting high‐yield visible and near‐IR emission that are synthesized via a single‐step microwave‐assisted hydrothermal technique with a single glucosamine‐HCl starting material (thiourea precursor used for NS‐GQDs). As‐synthesized N‐GQDs and NS‐GQDs are well‐dispersed (average sizes of 5.50 and 3.90 nm) with high crystallinity and pronounced G‐band. Formed by the bottom‐up assembly of glucosamine, they contain amine linkage and a variety of oxygen‐containing functional groups assessed by Fourier‐transform infrared spectroscopy with ≈2% sulfur for NS‐GQDs. The synthetic procedure allows varying their size and the bandgap. Unlike other graphene‐based quantum dots, these GQDs exhibit bright, stable fluorescence both in the visible and near‐IR with high quantum yields of up to 60%. Excitation‐dependent visible fluorescence is attributed to size‐dependent bandgaps, with near‐IR emission potentially arising from the emissive defect states/their arrangements. Advantageous properties of these GQDs are utilized to develop exciton recombination layer for organic light‐emitting devices exhibiting both photoluminescence and electroluminescence in the visible. Produced by ecofriendly one‐step scalable synthesis brightly‐emissive N‐GQDs and NS‐GQDs become a promising material for novel organic optoelectronics.

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Graphene oxide (GO) is a graphene derivative that emits fluorescence, which makes GO an attractive material for optoelectronics and biotechnology. In this work, we utilize ozone treatment to controllably tune the band gap of GO, which can significantly enhance its applications. Ozone treatment in aqueous GO suspensions yields the addition/rearrangement of oxygen-containing functional groups suggested by the increase in vibrational transitions of C-O and C=O moieties. Concomitantly it leads to an initial increase in GO fluorescence intensity and significant (100 nm) blue shifts in emission maxima. Based on the model of GO fluorescence originating from sp2 graphitic islands confined by oxygenated addends, we propose that ozone-induced functionalization decreases the size of graphitic islands affecting the GO band gap and emission energies. TEM analyses of GO flakes confirm the size decrease of ordered sp2 domains with ozone treatment, whereas semi-empirical PM3 calculations on model addend-confined graphitic clusters predict the inverse dependence of the band gap energies on sp2 cluster size. This model explains ozone-induced increase in emission energies yielding fluorescence blue shifts and helps develop an understanding of the origins of GO fluorescence emission. Furthermore, ozone treatment provides a versatile approach to controllably alter GO band gap for optoelectronics and bio-sensing applications.

Graphene possesses a number of advantageous properties, however, does not exhibit optical emission, which limits its use in optoelectronics. Unlike graphene, its functional derivative, graphene oxide (GO) exhibits fluorescence emission throughout the visible. Here, we focus on controlled methods for tuning the optical properties of GO. We introduce ozone treatment of reduced graphene oxide (RGO) in order to controllably transform it from non-emissive graphene-like material into GO with a specific fluorescence emission response. Solution-based treatment of RGO for 5-45 min with ∼1.2 g l ozone/oxygen gas mixture yields a drastic color change, bleaching of the absorption in the visible and the stepwise increase in fluorescence intensity and lifetime. This is attributed to the introduction of oxygen-containing functional groups to RGO graphitic platform as detected by the infrared spectroscopy. A reverse process: controllable quenching of this fluorescence is achieved by the thermal treatment of GO in aqueous suspension up to 90 °C. This methodology allows for the wide range alteration of GO optical properties starting from the dark-colored non-emissive RGO material up to nearly transparent highly ozone-oxidized GO showing substantial fluorescence emission. The size of the GO flakes is concomitantly altered by oxidation-induced scission. Semi-empirical PM3 theoretical calculations on HyperChem models are utilized to explore the origins of optical response from GO. Two models are considered, attributing the induced emission either to the localized states produced by oxygen-containing addends or the islands of graphitic carbon enclosed by such addends. Band gap values calculated from the models are in the agreement with experimentally observed transition peak maxima. The controllable variation of GO optical properties in aqueous suspension by ozone and thermal treatments shown in this work provides a route to tune its optical response for particular optoelectronics or biomedical applications.

Nitrogen-doped graphene quantum dots (NGQDs) synthesized from a single glucosamine precursor are utilized to develop a novel UV photodetector. Optical properties of NGQDs can be altered with short- (254 nm), mid- (302 nm), and long-wave (365 nm) ultraviolet (UV) exposure leading to the reduction of absorption from deep to mid UV (200–320 nm) and enhancement above 320 nm. Significant quenching of blue and near-IR fluorescence accompanied by the dramatic increase of green/yellow emission of UV-treated NGQDs can be used as a potential UV-sensing mechanism. These emission changes are attributed to the reduction of functional groups detected by Fourier transformed infrared spectroscopy and free-radical-driven polymerization of the NGQDs increasing their average size from 4.70 to 11.20 nm at 60 min treatment. Due to strong UV absorption and sensitivity to UV irradiation, NGQDs developed in this work are utilized to fabricate UV photodetectors. Tested under long-/mid-/short-wave UV, these devices show high photoresponsivity (up to 0.59 A/W) and excellent photodetectivity (up to 1.03 × 1011 Jones) with highly characteristic wavelength-dependent reproducible response. This study suggests that the optical/structural properties of NGQDs can be controllably altered via different wavelength UV treatment leading us to fabricate NGQD-based novel UV photodetectors providing high responsivity and detectivity.