Hall Effect in Polycrystalline Organic Semiconductors: The Effect of Grain Boundaries

Highly crystalline thin films in organic semiconductors are important for applications in high-performance organic optoelectronics. Here, the effect of grain boundaries on the Hall effect and charge transport properties of organic transistors based on two exemplary benchmark systems is elucidated: (1) solution-processed blends of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C₈-BTBT) small molecule and indacenodithiophene-benzothiadiazole (C₁₆IDT-BT) conjugated polymer, and (2) large-area vacuum evaporated polycrystalline thin films of rubrene (C₄₂H₂₈). It is discovered that, despite the high field-effect mobilities of up to 6 cm² V⁻¹ s⁻¹ and the evidence of a delocalized band-like charge transport, the Hall effect in polycrystalline organic transistors is systematically and significantly underdeveloped, with the carrier coherence factor α < 1 (i.e., yields an underestimated Hall mobility and an overestimated carrier density). A model based on capacitively charged grain boundaries explaining this unusual behavior is described. This work significantly advances the understanding of magneto-transport properties of organic semiconductor thin films.