Aggregation-Tuned Charge Transport and Threshold Voltage Modulation in Poly(3-hexylthiophene) Field-Effect Transistors

In this report, a thickness-driven, aggregation-structure-transport optimum in sonicated poly(3-hexylthiophene) (P3HT) FETs was investigated. Mobility peaks at ~10-20 nm, coincident with a minimum in the photoluminescence (PL) vibronic ratio I0-0/I0-1 (strong <i>H</i>-aggregate interchain coupling) and X-ray diffraction sharpening of the (100) lamellar peak with slightly reduced <i>d</i>-spacing, indicate tighter π-π stacking and larger crystalline coherence. Absorption analysis (Spano model) is consistent with this enhanced interchain order. The mobility maximum arises from an optimal balance: <i>J</i>-aggregate-like intrachain planarity supports along-chain transport, while <i>H</i>-aggregates provide interchain connectivity for efficient hopping. Below this thickness, insufficient interchain coupling limits transport; above it, over-aggregation and disorder introduce traps and weaken gate control. The sharp rise in threshold voltage beyond the critical thickness indicates more trap states or fixed charges forming within the film bulk. As a result, a larger gate bias is needed to deplete the channel (remove excess holes) and switch the device off. These results show that electrical gating can be tuned via solution processing (sonication) and film thickness-guiding the design of P3HT devices for photovoltaics and sensing.