This paper reports the performance of drop-on-demand piezo-activated microdroplet generation investigated using microdroplet cavity enhanced fluorescence spectroscopy. Aqueous microdroplets, doped with a fluorescent dye, exhibit fluorescence spectra that are dominated by cavity resonances (termed whispering gallery modes) that, when analysed using Mie theory, allow for the determination of the radius of each microdroplet. The effect of controlled changes in the square-wave droplet generator voltage waveform on droplet size is investigated as well as the size reproducibility of successive microdroplets. Furthermore, using custom square-wave waveforms, microdroplet radii spanning ∼10 to 30 μm are produced from the same droplet dispenser. These non-standard waveforms do not sacrifice the reproducibility of microdroplet generation with \u3c1% size variation. Tuning the single square-wave pulsewidths induces predictable changes in the microdroplet radius and steps on the order of tens of nanometers are detectable. With finer voltage adjustments the microdroplet size is essentially tunable. These results confirm the extremely high stability and reproducibility of on-demand microdroplet generation and that precise size control is possible, rendering them suitable platforms for many applications in fundamental and applied research in areas including mass spectrometry, aerosol investigations and liquid-phase chemistry
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