We present a new method for increasing the resolution of direct femtosecond laser writing by multiphoton polymerization, based on quencher diffusion. This method relies on the combination of a mobile quenching molecule with a slow laser scanning speed, allowing the diffusion of the quencher in the scanned area and the depletion of the multiphoton-generated radicals. The material we use is an organic-inorganic hybrid, while the quencher is a photopolymerizable amine-based monomer which is bound on the polymer backbone upon fabrication of the structures. We use this method to fabricate woodpile structures with a 400 nm intralayer period. This is comparable to the results produced by direct laser writing based on stimulated-emission-depletion microscopy, the method considered today as state-of-the-art in 3D structure fabrication. We optically characterize these woodpiles to show that they exhibit well-ordered diffraction patterns and stopgaps down to near-infrared wavelengths. Finally, we model the quencher diffusion, and we show that radical inhibition is responsible for the increased resolution.

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.

The fabrication of fully three-dimensional photonic crystals with a bandgap at optical wavelengths is demonstrated by way of direct femtosecond laser writing of an organic-inorganic hybrid material with metal-binding moieties, and selective silver coating using electroless plating. The crystals have 600-nm intralayer periodicity and sub-100 nm features, and they exhibit well-defined diffraction patterns.

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.

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