Understanding the evolution of the Raman spectra of molecularly p-doped poly(3-hexylthiophene-2,5-diyl): signatures of polarons and bipolarons

Molecular doping is a key process to increase the density of charge carriers in organic semiconductors. Doping-induced charges in polymer semiconductors result in the formation of polarons and/or bipolarons due...

Structural and Electrical Conductivity Studies of PVDF-HFP Film Filled with Tio2 and Nacl for Polymer Semiconductors

As prospective electrolyte membranes are fabricated using a conducting copolymer of poly (vinylidene difluoride-co-hexaf luoropropy lene) (PVDF-HFP) by a solution casting method. The prepared membranes were filled with an electrical conductor (NaCl) and semiconductor (TiO2) nanopowder in this method. The assimilated membranes were analytically characterized by scanning electron microscope (SEM) for surface morphology and X-ray diffraction (XRD) for crystalline nature of the TiO2 nanopowder present in the prepared membrane. The FTIR confirms the structural analysis of the copolymer and the NaCl and TiO2 incorporation nature into the PVDF-HFP membrane. Electrochemical stability of the fabricated membrane of PVDF-HFP was performed using thermo-gravimetric analysis (TGA). The cyclic voltammetric analysis conducted the charge and discharge tests of the filled and unfilled membrane. The addition of nano TiO2 particles and NaCl to the copolymer membrane was found to reduce the PVDF-HFP membrane's porousness and improve the ion conductivity and electrolyte/electrode interfacial stability of the filled membrane.

Improvement of poly(3-hexylthiophene-2,5-diyl) electron mobility through complete elimination of regioregularity defects

The improvement of electron transport in polymer semiconductors is highly desirable for realizing robust, large-area and low-cost organic integrated circuits. This work investigates the effect of regioregularity on the intrinsic hole and electron transport characteristics of poly(3-hexylthiophene-2,5-diyl) (P3HT) using current-voltage (I-V) measurements in metal/polymer/metal sandwich structures. Through a direct comparison between 93% regioregular P3HT (EG-P3HT) and 100% regioregular defect-free poly(3-hexylthiophene-2,5-diyl) (DF-P3HT), it is found that the elimination of regioregularity defects improves the electron mobility of DF-P3HT (1.05 × 10-7 cm2 V-1 s-1) by three orders of magnitude compared to the 93% regioregular EG-P3HT sample (1.82 × 10-10 cm2 V-1 s-1). Quantum chemical calculations indicate that the improvement of electron mobility in DF-P3HT can be associated to the lower degree of disorder in these samples that tends to increase the transfer angle between the lowest unoccupied molecular orbitals of adjacent chains. At the same time, the lower dipole moments produced by the defect-free polymer molecules also appears to play an important role in decreasing the susceptibility of charge transport to environment-induced electron traps. The obtained results provide a strong evidence that the elimination of regioregularity defects is an effective technique to improve electron transport and restore the symmetry between hole and electron mobility in P3HT as well as other thiophene-based polymers.