Controlling the pn-type behavior of a semiconductor such as silicon by adding an extremely small quantity of an impurity (doping) is a central part of inorganic semiconductor electronics since the 20th century. Recent progress in the doping of organic semiconductors strongly suggests the advent of a new era of doped organic semiconductors. Here, the principles and effects of doping at the level of parts per million (ppm) in organic semiconductor films and single crystals are described, including descriptions of complete pn-control, doping sensitization, ppm doping using an extremely low-speed deposition technique reaching 10-9 nm s-1 , and emerging ppm-level doping effects, such as trap filling, majority carriers, homojunction formation, and decreased mobility, as well as ppm-level doping effects in organic single crystals measured by the Hall effect, which shows a doping efficiency of 24%. The Wannier excitonic doping of organic single crystals possessing band conduction and the defect science of organic single crystals related to carrier trapping and scattering are introduced as a new scientific field. The dawn of organic single-crystal electronics is also discussed.
Keywords: Hall effects; doping efficiencies; organic semiconductor films; organic single crystals; ppm-level doping.
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