Atomically precise graphene quantum dots synthesized by bottom-up chemistry are promising versatile single emitters with potential applications for quantum photonic technologies. Toward a better understanding and control of graphene quantum dot (GQD) optical properties, we report on single-molecule spectroscopy at cryogenic temperature. We investigate the effect of temperature on the GQDs’ spectral linewidth and vibronic replica, which we interpret building on density functional theory calculations. Finally, we highlight that the vibronic signatures are specific to the GQD geometry and can be used as a fingerprint for identification purposes.

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