We report in situ high-resolution transmission electron microscopy observing the shrinkage of single-layer giant fullerenes (GF). At temperatures $\sim 2000°\mathrm{C}$, the GF volume reduces by greater than one 100-fold while the fullerene shell remains intact, evolving from a slightly polygonized to a nearly spherical shape with a smaller diameter. The number of carbon atoms in the GF decreases linearly with time until the small subbuckyball cage opens and rapidly disappears. Theoretical modeling indicates that carbon atoms are removed predominantly from the weakest binding energy sites, i.e., the pentagons, leading to the constant evaporation rate. The fullerene cage integrity is attributed to the collective behavior of interacting defects. These results constitute the first experimental evidence for the “shrink-wrapping” and “hot-giant” fullerene formation mechanisms.

• Received 31 July 2007

DOI:https://doi.org/10.1103/PhysRevLett.99.175503