Anisotropic PCL nanofibers embedded with nonlinear nanocrystals as strong generators of polarized second harmonic light and piezoelectric currents†
Using the electrospinning technique nanofibers consisting of organic nonlinear optical 3-nitroaniline (3NA, C6H6N2O2) nanocrystals embedded in poly-ε-caprolactone (PCL) polymer, 3NA@PCL nanofibers, were produced. Polarimetry optical second harmonic generation and X-ray diffraction studies show that 3NA push–pull molecules crystallize inside the polymer fibers with a strong preferential orientation giving rise to an alignment of the molecular dipole moments along the nanofibers longitudinal axis. This alignment strongly enhances the second order nonlinear optical response of the fibers. Intense second harmonic generation emission was observed from a single nanofiber, corresponding to an effective second order susceptibility of 80 pm V−1, four times greater than the largest second order susceptibility tensor element (21 pm V−1) associated with a macroscopic 3NA crystal. Moreover, when subjected to a modest periodically applied force of 3 N, a piezoelectric current of 70 nA generated by a 4 cm2 electrospun nanofiber mat amounted to 122 nW cm−2 of instantaneous density power, sufficient to power a LCD display. The results show that the electrospinning technique is a powerful technique to fabricate organic functional materials with oriented nanocrystals made of highly polarizable molecules, embedded in a polymer matrix.