Tuned longitudinal surface plasmon resonance and third-order nonlinear optical properties of gold nanorods

In order to elucidate the relationship for third-order nonlinear optical properties of anisotropic metal nanoparticles between the incident laser wavelength and surface plasmon resonance (SPR) wavelength, gold nanorods (GNRs) with a tuned longitudinal SPR mode in frequency were prepared by seed-mediated methods with two different surfactants, cetyltrimethylammonium bromide (CTAB) and benzyldimethylammonium chloride (BDAC). The real and imaginary parts of the third-order nonlinear optical susceptibilities χ(3) were examined by near-infrared (800 nm) femtosecond Z-scan and I-scan techniques for various gold sols with SPR wavelengths of 530 nm (spheres), 800 nm (nanorods) and 1000 nm (nanorods), named as 530GNSs, 800GNRs and 1000GNRs, respectively. All the samples showed intrinsically third-order nonlinear optical refractive responses. However, as for the real part of χ(3) for one particle, 800GNRs whose plasmon peak was tuned to the incident laser wavelength exhibited a Reχ(3) value 45 times stronger than 530GNSs. More interestingly, the imaginary part of χ(3) was more greatly influenced at the tuned SPR wavelength. Here we first demonstrate that 800GNRs showed plasmon-enhanced saturable absorption (SA) due to a longitudinal SPR tuned to the incident laser wavelength.