The excited-state dynamics of J aggregates of PIC have been studied by means of picosecond and subpicosecond absorption spectroscopy as well as integrated fluorescence yield measurements. The results of these measurements show that both the lifetime and the fluorescence yield are strongly dependent on excitation pulse intensity. At relatively high light intensity (1014 photons cm−2 pulse−1) the S1 lifetime is essentially pulse limited (<1 ps) and the fluorescence yield is very low. Upon decreasing the light intensity a gradual increase of the excited-state lifetime and fluorescence yield is observed. At very low excitation intensity (1010 photons cm−2 pulse−1) a single exponential lifetime of 400 ps is observed. At intermediate intensities the excited-state decay is strongly nonexponential. The observed intensity dependence of the excited-state dynamics is attributed to efficient exciton–exciton annihilation between the highly mobile singlet excitons. By applying an expression for bimolecular exciton annihilation, derived and used for photosynthetic antenna systems [Paillotin et al., Biophys. J. 25, 513 (1979)], and treating the energy migration as a hopping motion, information about aggregate size and exciton hopping rate was obtained.

Three-dimensional (3D) micro/nano-structuring of photo-resists is systematically studied at the close-to-dielectric- breakdown irradiance. It is demonstrated that avalanche absorption is playing a major part in free electron generation and chemical bond breaking at these conditions. The steps of photo-initiation and chemical bond breaking in propagation of polymerization are altered as compared with photo-polymerization at low-irradiance and one-photon stereo-lithography. The avalanche dominates radical generation and promotion of polymerization at tight focusing and a high approximately TW/cm(2) irradiance. The rates of electron generation by two-photon absorption and avalanche are calculated for the experimental conditions. Simulation results are corroborated by 3D polymerization in three resists with different photo-initiators at two different wavelengths and pulse durations. The smallest feature sizes of 3D polymerized logpile structures are consistent with spectral dependencies of the two photon nonlinearities. Implications of these findings for achieving sub-100 nm resolution in 3D structuring of photo-polymers are presented.

The femtosecond laser-induced multi-photon polymerization of a zirconium–silicon based sol–gel photopolymer was employed for the fabrication of a series of micro-optical elements with single and combined optical functions: convex and Fresnel lenses, gratings, solid immersion lenses on a glass slide and on the tip of an optical fiber. The microlenses were produced as polymer caps of varying radii from 10 to 90  µm. The matching of refractive indices between the polymer and substrate was exploited for the creation of composite glass-resist structures which functioned as single lenses. Using this principle, solid immersion lenses were fabricated and their performance demonstrated. The magnification of the composite solid immersion lenses corresponded to the calculated values. The surface roughness of the lenses was below ∼ 30 nm, acceptable for optical applications in the visible range. In addition, the integration of micro-optical elements onto the tip of an optical fiber was demonstrated. To increase the efficiency of the 3D laser polymerization, the lenses were formed by scanning only the outer shell and polymerizing the interior by exposure to UV light.

We report a study of the determination of polymer cross-linking, namely the degree of conversion and refractive index of the microstructures created by two-photon polymerization (TPP). The influence of TPP processing parameters such as laser intensity and scanning velocity is investigated. The degree of conversion is analyzed via Raman microspectroscopy and the refractive index is measured with the interferometric technique employing a Michelson interferometer. Moreover, the relationship between these two properties is revealed and details are discussed. The largest refractive index change that we have obtained is of the order of 10 −2 . Finally, we propose and demonstrate experimentally the realization of the gradientindex (GRIN) structure, resulting from a laser-induced local refractive index modification due to monomer cross-linking, i.e. degree of conversion. This work implies that the TPP technique is a valuable tool for the fabrication of GRIN microoptics for (in)homogeneous molding of light flow at the micrometer scale.

Light-initiated quasi-instant solidification of a liquid polymer is attractive for its ultra-precise spatial and temporal control of the photochemical reaction. In this paper we present microlenses structured by femtosecond laser-induced photopolymerization. Due to nonlinear phenomena the fabrication resolution is not restricted to the diffraction limit for the applied laser excitation wavelength but is determined by the intensity of a focused beam. Furthermore, pin-point structuring enables one to produce three-dimensional structures of any form from the photopolymer. The smallest structural elements of 200 nm lateral dimensions can be achieved reproducibly by using high numerical aperture oil immersion focusing optics (NA = 1.4). Axial resolution (which is fundamentally a few times worse than lateral resolution due to the distribution of light intensity in the focal region) can be controlled to a precision of a few hundred nanometers by decreasing the scanning step. In our work we applied the commercially available and widely used zirconium–silicon based hybrid sol–gel photopolymer (Ormosil, SZ2080). Arrays of custom-parameter spherical microlenses for microscopy applications have been fabricated. Their surface roughness, focal distance and imaging quality were tested. The obtained results show potential for fast and flexible fabrication of custom-parameter microlenses by the proposed technique.