Entropy-ruled nonequilibrium charge transport in thiazolothiazole-based molecular crystals: a quantum chemical study

The charge and energy fluctuations in molecular solids are crucial factors for a better understanding of charge transport (CT) in organic semiconductors. The energetic disorder-coupled molecular charge transport is still not well-established. Moreover, the conventional Einstein's diffusion (D)-mobility (μ) relation fails to explain the quantum features of organic semiconductors, including nonequilibrium and degenerate transport systems, where k_B is the Boltzmann constant, T is the temperature and q is the electric charge. To overcome this issue, a unified version of the entropy-ruled D/μ relation was proposed by Navamani (J. Phys. Chem. Lett., 2024, 15, 2519-2528) for hopping and band transport systems as where d, η and h_eff are the dimension (d = 1, 2, 3), chemical potential and effective entropy, respectively. Within this context, we investigate the CT properties of 2,5-bis(4-methoxyphenyl)thiazolo[5,4-d]thiazole (MOP-TZTZ) and 2,5-bis(2,4,5 trifluorophenyl)-thiazolo[5,4-d]thiazole (TFP-TZTZ) molecular solids using electronic structure calculations and the entropy-ruled method. The CT key parameters such as charge transfer integral and site energy are computed by matrix elements of the Kohn-Sham Hamiltonian. Using Marcus theory, the charge transfer rate is numerically calculated for MOP-TZTZ and TFP-TZTZ molecular crystals under different site energy disorder (ΔE(E⃑)) situations. Using our entropy-ruled method, the exact diffusion-mobility (D/μ) and other transport quantities such as thermodynamic density of states, conductivity, and current density are calculated for these derivatives at different applied electric field values via the site energy disorder. The theoretical results show that the molecule TFP-TZTZ has good hole mobility (∼0.012 cm² V^-1 s^-1) at a site energy disorder value of 90 meV. The obtained ideality factor from the Navamani-Shockley diode current density equation categorizes the typical transport as either the Langevin-type or Shockley-Read-Hall mechanism in the studied molecular solids. Our analysis clearly shows that both the electron and hole transport in these MOP-TZTZ and TFP-TZTZ molecules follow the trap-free Langevin mechanism, which is indeed ideal for designing charge-transporting molecular devices.