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.
Synthetic diamond
Numerous claims of diamond synthesis were documented between 1879 and 1928; most of those attempts were carefully analyzed but none were confirmed. In the 1940s, systematic research began in the United States, Sweden and the Soviet Union to grow diamonds using CVD and HPHT processes. The first reproducible synthesis was reported around 1955. Those two processes still dominate the production of synthetic diamond. A third method, known as detonation synthesis, entered the diamond market in the late 1990s. In this process, nanometer-sized diamond grains are created in a detonation of carbon-containing explosives. A fourth method, treating graphite with high-power ultrasound, has been demonstrated in the laboratory, but currently has no commercial application.