THICKNESS DEPENDENCE OF THIRD-HARMONIC GENERATION FROM SELF-ASSEMBLED REGIOREGULAR POLY(3-HEXYLTHIOPHENE) THIN FILMS ON QUARTZ GLASSES WITH DIFFERENT SURFACES
Regioregular poly(3-hexylthiophene) [RR-P3HT] thin films were prepared on fused quartz glasses by spin-coating and drop-casting from the chloroform solutions. Film structures and morphologies were characterized by UV-visible absorption spectra, out-of-plane X-ray diffraction (XRD) and atomic force microscopy (AFM). Drop-cast films showed increased χ(3) of about three times higher than that of the spin-coated ones when the film thicknesses were both around 140 nm, and the magnitude of the increase was different for different thickness. The magnitudes of χ(3) for drop-cast RR-P3HT films were calculated in the range of 10-11 esu, and the phases of χ(3) lay in the range from 230 to 300° which were consistent with the contributions from two-photon absorptions (TPA). Hexamethyldisilazane (HMDS) treatment of the glass substrates could increase the χ(3) of drop-cast films further from about ten percent to several times higher. This also depended on the film thickness. These results revealed the deposition method and surface modification effects on the self-assembled RR-P3HT film structures, and the importance of higher-ordering and increased crystallinity for the enhancement of the χ(3) of the polymeric films for their applications in NLO devices.