Quantum dot based 3D printed woodpile photonic crystals tuned for the visible.

The development of dynamically responsive 3D photonic elements, which is crucial for the design of active integrated photonic circuits, requires the incorporation of material systems with fast and tunable response. To this end, semiconductor quantum dots have been widely used to perform as the active material system to be integrated; nonetheless, multiple-step processing is usually required for the active functions to be preserved, thereby restricting functionality of integrated 3D quantum photonic elements mostly to the infrared. Here, we report a simple scheme for the realization of visible light active 3D photonic devices by combining direct laser writing with two-photon absorption and in situ synthesis of cadmium sulfide (CdS) nanoparticles. The novel active 3D printable hybrid material is synthesized by crosslinking precursors of CdS quantum dots into a photo-structurable organic-inorganic zirconium-silicon hybrid composite integrating functional properties of both high spatial resolution and high third-order nonlinearity into the photonic matrix. As a proof-of-demonstration for 3D printed active photonic devices, woodpile photonic crystals with an inlayer periodicity down to 500 nm are successfully fabricated showing clear photonic stop bands in the visible spectral region, while for the first time, evidence of an ultrafast dynamic response in the visible is also demonstrated.

Redox multiphoton polymerization for 3D nanofabrication.

We report for the first time on the redox multiphoton polymerization of an organic-inorganic composite material, in which one of the components, a vanadium metallo-organic complex, initiates the polymerization. The composite employs multiphoton absorption to self-generate radicals by photoinduced reduction of the metal species from vanadium (V) to vanadium (IV). We exploit this material for the fabrication of fully 3D structures by multiphoton polymerization with 200 nm resolution, employing a femtosecond laser operating at 800 nm, in the absence of a photoinitiator. Nonlinear absorption measurements indicate that the use of an 800 nm laser initiates the photopolymerization due to three-photon absorption of the vanadium alkoxide. The laser power required to induce this three-photon polymerization is comparable to what is required for inducing two-photon polymerization in materials using standard two-photon absorbers, most likely due to the high content of vanadium in the final composite (up to 50% mole).

Diffusion-assisted high-resolution direct femtosecond laser writing.

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.