Size and chemistry of 1–2 layer graphene nanosheets at the transition into photoluminescence and assembly with large shifts from blue to red emission

• Edge-modified 1–2 layer graphene was photoluminescent when ≤ 15 nm lateral size. • Large red shifts from blue through to orange / red emission depended on edge charge. • Positively-charged edge amines overcame negative face charge in self-assembly. • Oxidation into carboxyl groups strongly weakened the red shift. • Repulsion at negatively-charged edges and faces hindered red-shifting assembly. Synthetic refinement of graphene photoluminescence remains challenging because underlying characteristics have not been well understood from polydisperse mixtures of different sizes and surface chemistries. Here, we isolate and characterise different populations of 1–2 layer graphene (1-2LG) each with narrow size range. Small 1-2LG nanosheets down to 25 nm size remained black and non-luminescent with N . and O . additions at their edges, whereas 15 nm nanosheets transitioned into photoluminescence, while retaining substantial sp 2 carbon of graphene. Positively-charged amine modifications overcame the repulsion between nanosheets from the negative zeta potential of sp 2 graphene faces in water and allowed assembly of similarly-sized nanosheets with large red shifts (>150 nm) taking blue emission into the red. However, more extensive edge modification into carboxyl groups and neutral amides built negative charge at the edges. Together with smaller nanosheet size and reduced sp 2 carbon, red shifts were weakened by half in these isolates, which were most modified and more like graphene oxide and carbon quantum dots. N addition to form amines at nanosheet edges, while avoiding O atom addition and carboxyl groups, presents as a simple refinement for synthesis of self-assembling graphene quantum dots with multi-colour emission, which also retain sp 2 carbon properties of graphene.