The research, reported as the cover article in the May 4 issue of the Journal of Physical Chemistry C ("Ethene to Graphene: Surface Catalyzed Chemical Pathways, Intermediates, and Assembly"), was conducted by scientists at the Georgia Institute of Technology, Technische Universität München in Germany, and the University of St. Andrews in Scotland. In the United States, the research was supported by the U.S. Air Force Office of Scientific Research and the U.S. Department of Energy's Office of Basic Energy Sciences.

"Since graphene is made from carbon, we decided to start with the simplest type of carbon molecules and see if we could assemble them into graphene," explained Uzi Landman, a Regents' Professor and F.E. Callaway endowed chair in the Georgia Tech School of Physics who headed the theoretical component of the research. "From small molecules containing carbon, you end up with macroscopic pieces of graphene."

Graphene is now produced using a variety of methods including chemical vapor deposition, evaporation of silicon from silicon carbide - and simple exfoliation of graphene sheets from graphite. A number of earlier efforts to produce graphene from simple hydrocarbon precursors had proven largely unsuccessful, creating disordered soot rather than structured graphene.

Guided by a theoretical approach, the researchers reasoned that the path from ethene to graphene would involve formation of a series of structures as hydrogen atoms leave the ethene molecules and carbon atoms self-assemble into the honeycomb pattern that characterizes graphene. To explore the nature of the thermally-induced rhodium surface-catalyzed transformations from ethene to graphene, experimental groups in Germany and Scotland raised the temperature of the material in steps under ultra-high vacuum. They used scanning-tunneling microscopy (STM), thermal programed desorption (TPD) and high-resolution electron energy loss (vibrational) spectroscopy (HREELS) to observe and characterize the structures that form at each step of the process.

Upon heating, ethene adsorbed onto the rhodium catalyst evolves via coupling reactions to form segmented one-dimensional polyaromatic hydrocarbons (1D-PAH). Further heating leads to dimensionality crossover - one dimensional to two dimensional structures - and dynamical restructuring processes at the PAH chain ends with a subsequent activated detachment of size-selective carbon clusters, following a mechanism revealed through first-principles quantum mechanical simulations. Finally, rate-limiting diffusional coalescence of these dynamically self-evolved cluster-precursors leads to condensation into graphene with high purity.

At the final stage before the formation of graphene, the researchers observed nearly round disk-like clusters containing 24 carbon atoms, which spread out to form the graphene lattice. "The temperature must be raised within windows of temperature ranges to allow the requisite structures to form before the next stage of heating," Landman explained. "If you stop at certain temperatures, you are likely to end up with coking."