Measuring the Pores’ Structure in P3HT Organic Polymeric Semiconductor Films Using Interface Electrolyte/Organic Semiconductor Redox Injection Reactions and Bulk Space-Charge

The article is another in a series of follow-up articles on the new spectroscopic method Energy Resolved–Electrochemical Impedance Spectroscopy (ER-EIS) and presents a continuation of the effort to explain the method for electronic structure elucidation and its possibilities in the study of organic polymeric semiconductors. In addition to the detailed information on the electronic structure of the investigated organic semiconductor, the paper deals with three of the hitherto not solved aspects of the method, (1) the pores structure, which has been embedded in the evaluation framework of the ER-EIS method and shown, how the basic quantities of the pores structure, the volume density of the pores’ density coefficient β = (0.038 ± 0.002) nm(−1) and the Brunauer-Emmet-Teller surface areas SABET SA == 34.5 m(2)g(−1) may be found by the method, here for the archetypal poly(3-hexylthiophene-2,5-diyl) (P3HT) films. It is next shown, why the pore’s existence needs not to endanger the spectroscopic results of the ER-EIS method, and a proper way of the ER-EIS data evaluation is presented to avoid it. It is highlighted (2), how may the measurements of the pore structure contribute to the determination of the, for the method ER-EIS important, real rate constant of the overall Marcus’ D-A charge-transfer process for the poreless material and found its value k(ct) (D-A) = (2.2 ± 0.6) × 10(−25) cm(4) s(−1) for P3HT films examined. It is also independently attempted (3) to evaluate the range of k(ct) (D-A), based on the knowledge of the individual reaction rates in a chain of reactions, forming the whole D-A process, where the slowest one (organic semiconductor hopping transport) determines the tentative total result k(ct) (D-A) ≅ 10(−25) cm(4) s(−1). The effect of injection of high current densities by redox interface reactions in the bulk of OS with built-in pores structure may be very interesting for the design of new devices of organic electronics.