The concept of bandgap science of organic semiconductor films for use in photovoltaic cells, namely, high-purification, pn-control by doping, and design of the built-in potential based on precisely-evaluated doping parameters, is summarized. The principle characteristics of organic solar cells, namely, the exciton, donor (D)/acceptor (A) sensitization, and p-i-n cells containing co-deposited and D/A molecular blended i-interlayers, are explained. ‘Seven-nines’ (7N) purification, together with phase-separation/cystallization induced by co-evaporant 3^rd molecules allowed us to fabricate 5.3% efficient cells based on 1 µm-thick fullerene:phthalocyanine (C₆₀:H₂Pc) co-deposited films. pn-control techniques enabled by impurity doping for both single and co-deposited films were established. The carrier concentrations created by doping were determined by the Kelvin band mapping technique. The relatively high ionization efficiency of 10% for doped organic semiconductors can be explained by the formation of charge transfer (CT)-complexes between the dopants and the organic semiconductor molecules. A series of fundamental junctions, such as Schottky junctions, pn-homojunctions, p⁺, n⁺-organic/metal ohmic junctions, and n⁺-organic/ p⁺-organic ohmic homojunctions, were fabricated in both single and co-deposited organic semiconductor films by impurity doping alone. A tandem cell showing 2.4% efficiency was fabricated in which the built-in electric field was designed by manipulating the doping.