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
Scientists theorized about graphene for years. It had been produced unintentionally in small quantities for centuries through the use of pencils and other similar graphite applications. It was observed originally in electron microscopes in 1962, but it was studied only while supported on metal surfaces. The material was later rediscovered, isolated, and characterized in 2004 by Andre Geim and Konstantin Novoselov at the University of Manchester. Research was informed by existing theoretical descriptions of its composition, structure, and properties. This work resulted in the two winning the Nobel Prize in Physics in 2010 "for groundbreaking experiments regarding the two-dimensional material graphene."