Photomultiplication in conventional inorganic semiconductors has been known and used for decades, the underlying mechanism being multiplication by impact ionization triggered by hot carriers. Since neither carrier heating by an electric field nor avalanche multiplication are possible in strongly disordered organic solids, charge multiplication seems to be highly unlikely in these materials. However, here the photomultiplication observed in the bulk of a unipolar disordered organic semiconductor is reported. The proportion of extracted carriers to incident photons is experimentally determined to be in excess of 3000 % in a single‐layer device of the air‐stable, n‐type organic semiconductor F16CuPc (Pc: phthalocyanine). This effect is explained in terms of exciton quenching by localized charges, the subsequent promotion of these detrapped charges to the high‐mobility energy band of the density‐of‐states (DOS) distribution, and subsequent slow equilibration within this broad intrinsic DOS. Such a mechanism allows multiple replenishment of the optically released charge by mobile carriers injected from an Ohmic electrode. Also shown is photomultiplication in double‐layer devices composed of layers of donor and acceptor small‐molecule materials. This result implies that, apart from exciton dissociation at a donor/acceptor interface, exciton energy transfer to trapped carriers is a complementary photoconductivity process in organic solar cells. This new insight paves the way to cheap, highly efficient organic photodetectors on flexible substrates for numerous applications.

We report on organic light-emitting transistors with a submicron-channel length, gold source, and calcium drain contacts. The respective contact metals allow efficient injection of holes and electrons in the tetracene channel material. Transistor characteristics were measured in parallel with electroluminescence being recorded by a digital camera focused on the transistor channel. In the case of submicron-channel lengths, the transistor source-drain current at higher gate voltages was determined by the source-drain voltage. At larger channel lengths, the source-drain current was limited by the injection of electrons from the calcium contact, as hole ejection to this contact was fully blocked. The hole blocking is explained in terms of a chemical reaction occurring at the Ca/tetracene interface.

We show that current–voltage characteristics, measured on a tetracene crystal sandwiched between two gold electrodes, are in quantitative agreement with the concept of dopant-assisted charge injection across a metal–organic interface. This notion explains the wild range of carrier mobilities recently found by space-charge limited current measurements in apparently identical tetracene crystals [de Boer et al., J. Appl. Phys. 95, 1196 (2004)] and the difference between these data and the mobility measured in the time-of-flight experiments.

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