Molecular ordering of spin-coated and electrosprayed P3HT:PCBM thin films and their applications to photovoltaic cell

• An orientation of P3HT was controlled due to the solvent evaporation time.
• A solvent evaporation time was evaluated for the electrospray deposition.
• A crystallinity parameter was evaluated from the Raman spectroscopy.
• X-ray diffraction indicates the increased edge-on oriented P3HT.
• A photo conversion efficiency of2.0% was achieved without the annealing.

Poly(3-hexylthiophene-2,5-diyl) (P3HT) is one of the most popular donor polymers for organic photovoltaic cells; however, annealing-induced molecular ordering is necessary for realizing high photoconversion efficiency. In this study, the ratio of ordered-disordered P3HT Raman signals was calculated as the crystallinity parameter, which can be evaluated as the molecular ordering of P3HT. In the case of spin-coated devices, the crystallinity parameter increases with increasing annealing temperature, and this agrees with the photovoltaic performance. Furthermore, the direct molecular ordering of P3HT during electrospray deposition is reported, detailing the relation between the solvent evaporation time and the crystallinity of P3HT, and is evaluated by Raman spectroscopy and grazing incidence X-ray diffraction. To observe the solvent evaporation phenomena of the electropsray process, in situ measurement of solvent evaporation time was also successfully realized for the first time by placing a CCD camera below the substrate in electrospray deposition. The solvent evaporation time was controlled from 0.036 to 2.8 s by changing the applied voltage and solvent. By investigating the relationship between the solvent evaporation time and the molecular ordering of P3HT, the long solvent evaporation time caused the high crystallinity of P3HT. In addition, the population of P3HT crystallinity with an edge-on orientation also increased with increasing solvent evaporation time by evaluating the grazing incidence X-ray diffraction pattern, in good agreement with the estimated crystallinity from Raman spectroscopy. Finally, a photoconversion efficiency of 2.0% was achieved by electrospray deposition without post thermal annealing.