Graphene
The theory of graphene was first explored by Wallace in 1947 as a starting point for understanding the electronic properties of 3D graphite. The emergent massless Dirac equation was first pointed out by Semenoff, DiVincenzo and Mele. The earliest TEM images of few-layer graphite were published by Ruess and Vogt in 1948. An early, detailed study on few-layer graphite dates to 1962 when Boehm and colleagues reported producing monolayer flakes of reduced graphene oxide. Efforts to make thin films of graphite by mechanical exfoliation started in 1990, but nothing thinner than 50 to 100 layers was produced before 2004. Initial attempts to make atomically thin graphitic films employed exfoliation techniques similar to the drawing method. Multilayer samples down to 10 nm in thickness were obtained.
Graphene production techniques
In scanning tunneling microscopy (STM), a sharp tip scans the surface of a sample in a regime of such tip-sample distances that electrons can quantum tunneling from the tip to the sample surface or vice versa. STM can be performed in a constant current or a constant height mode. The low temperature STM measurements provide thermal stability, which is a requirement for high resolution imaging and spectroscopic analysis. The first atomically resolved images of graphene grown on a platinum substrate were obtained using STM in the 1990s.