Chlorine-Substituted N-Heteroacene Analogues Acting as Organic Semiconductors for Solution-Processed n-type Organic Field-Effect Transistors

High performance solution processable n-type organic semiconductor is an essential element to realize low-cost, all organic and flexible composite logic circuits. In the design of n-type semiconducting materials, tuning the LUMO level of compounds is a key point. As a strong electron withdrawing unit, the introduction of chlorine atom into the chemical structure can increase the electron affinity of the material and reduce the LUMO energy level. Here, a series chlorine substituted N-heteroacene analogues of 6,7,8,9-tetrachloro-4,11-bis(4-((2-ethylhexyl)oxy)phenyl)-1,2,5]thiadiazolo3,4-b]phenazine (O4Cl), 6,7,8,9-tetrachloro-4,11-bis(4-((2-ethylhexyl)thio)phenyl)-1,2,5]thiadiazolo3,4-b]phenazine (S4Cl), 1,2,3,4,8,9,10,11-octachloro-6,13-bis(4-((2-ethylhexyl)oxy)phenyl)quinoxalino2,3-b]phenazine (8Cl) and 12Cl have been synthesized and characterized. Solution-processed organic field-effect transistors (OFETs) based on these four compounds exhibit good electron mobilities of 0.04 cm² V⁻¹ s⁻¹, 0.01 cm² V⁻¹ s⁻¹, 2×10⁻³ cm² V⁻¹ s⁻¹ and 3×10⁻³ cm² V⁻¹ s⁻¹, respectively, under ambient conditions. The results suggest that these chlorine substituted π-conjugated N-heteroacene analogues are promising n-type semiconductors in OFET applications.