Carbon quantum dots (CQDs) show promise in optoelectronics as a light emitter due to simple synthesis, biocompatibility and strong tunable light emissions. However, CQDs commonly suffer from aggregation caused quenching (ACQ), inhibiting the full potential of these light emitters. Studies into different ideal light emitters have shown enhancements when converting common ACQ effects to aggregation induced emission (AIE) effects. We report CQD synthesis using citric acid and high/ low thiourea concentrations, or sample 2/1. These two CQDs exhibited AIE and ACQ PL effects, respectively. CQD characterizations and photoluminescence interrogations of CQD films and solutions revealed that these unique emission mechanisms likely arose from different S incorporations into the CQDs. Furthermore, it was discovered that sample 2 emitted electrochemiluminescence (ECL) more intensely than sample 1 in a homogenous solution with S 2 O 8 2− as a coreactant, due to aggregation and interactions of CQD species in solution. Very interestingly, sample 1's CQD film| S 2 O 8 2− system achieved an ECL efficiency of 26% and emitted roughly 26 times more efficiently than sample 2 in the same conditions. Predominant interfacial reactions and surface state emission produced intense white light with a correlated color temperature of 2000 K. Spooling ECL spectroscopy was utilized to investigate emission mechanisms. Sample 2's CQD film|TPrA system had four times higher ECL intensity than that of sample 1, most likely due to π-cation interactions leading to a strong CQD •+ stability, thereby, enhancing ECL. It is anticipated that ECL enhancement of CQD films or solutions by means of AIE will lead to wide CQD optoelectronic applications.
A carbon quantum dot (CQD) sample series was synthesized from citric acid and varying concentrations of thiourea. The highest (sample 1) and lowest (sample 2) concentrations of thiourea exhibited unique visual effects and electronic structures. X-ray excited optical luminescence (XEOL) along with UV-visible spectroscopy provided unique insight into the absorption and emission mechanisms of samples 1 and 2, where only sample 2 emitted XEOL. Sample 1 exhibited the commonly observed aggregation caused quenching (ACQ) effects in the solid state. While sample 2 displayed unique aggregation induced emissions (AIE) effects upon exciting the sample above the C K edge. The AIE and ACQ sample differences were suspected to be from S moiety differences arising from the varying thiourea concentrations during synthesis. Furthermore, x-ray absorption spectroscopy (XAS) in modes of total electron yields (TEY) and partial fluorescence yields (PFY) allowed the identification of specific core and surface states of the CQDs. It was discovered that thiophene moieties were uniquely formed in the AIE sample’s surface and not anywhere in the ACQ CQD sample. The thiophene surface functionality is believed to be a significant contributor to the AIE effects seen in the XEOL studies. Understanding and preventing the common CQD ACQ mechanism allows the application of CQDs in solid lighting applications.
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