Alexander Pikulin

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.

Effects of spherical mode coupling on near-field focusing by clusters of dielectric microspheres

Colloidal particle lens array (CPLA) proved to be an efficient near-field focusing device for laser nanoprocessing of materials. Within CPLA, spherical particles do not act as independent microlenses. Due to the coupling of the spherical modes, the field near the clusters of spherical microparticles cannot be calculated by means of the superposition of Mie solutions for individual spheres. In the paper, the electromagnetic field distributions near laser-irradiated clusters of dielectric microspheres with configurations that match the fragments of the close-packed CPLA are studied. It is shown that some practically important mode coupling effects can be understood in terms of an effective immersion medium formed for the spherical particle by its surrounding.

Colloidal particle lens arrays-assisted nano-patterning by harmonics of a femtosecond laser

We consider nanopatterning of dielectric substrates by harmonics of single powerful femtosecond pulses from a Ti:Sapphire laser. The nanopatterning is mediated by closely packed monolayers of polystyrene microspheres that act as microlenses at the surface. Observed modification of the material proceeds via ionization. By our theory, the second harmonic is more effective in multi-photon ionization and is better focused than the fundamental frequency which is effective in multiplying of the amount of free electrons via impact ionization. Experiments show that conversion of a part of the pulse energy into the second harmonic decreases the modification threshold and improves the localization of the structures. Optimization of the time offset between the harmonics could further improve the efficiency and quality of nanostructuring.

Femtosecond Laser Irradiation of Plasmonic Nanoparticles in Polymer Matrix: Implications for Photothermal and Photochemical Material Alteration

We analyze the opportunities provided by the plasmonic nanoparticles inserted into the bulk of a transparent medium to modify the material by laser light irradiation. This study is provoked by the advent of photo-induced nano-composites consisting of a typical polymer matrix and metal nanoparticles located in the light-irradiated domains of the initially homogeneous material. The subsequent irradiation of these domains by femtosecond laser pulses promotes a further alteration of the material properties. We separately consider two different mechanisms of material alteration. First, we analyze a photochemical reaction initiated by the two-photon absorption of light near the plasmonic nanoparticle within the matrix. We show that the spatial distribution of the products of such a reaction changes the symmetry of the material, resulting in the appearance of anisotropy in the initially isotropic material or even in the loss of the center of symmetry. Second, we analyze the efficiency of a thermally-activated chemical reaction at the surface of a plasmonic particle and the distribution of the product of such a reaction just near the metal nanoparticle irradiated by an ultrashort laser pulse.

3D Photonic Nanostructures via Diffusion-Assisted Direct fs Laser Writing

We present our research into the fabrication of fully three-dimensional metallic nanostructures using diffusion-assisted direct laser writing, a technique which employs quencher diffusion to fabricate structures with resolution beyond the diffraction limit. We have made dielectric 3D nanostructures by multiphoton polymerization using a metal-binding organic-inorganic hybrid material, and we covered them with silver using selective electroless plating. We have used this method to make spirals and woodpiles with 600 nm intralayer periodicity. The resulting photonic nanostructures have a smooth metallic surface and exhibit well-defined diffraction spectra, indicating good fabrication quality and internal periodicity. In addition, we have made dielectric woodpile structures decorated with gold nanoparticles. Our results show that diffusion-assisted direct laser writing and selective electroless plating can be combined to form a viable route for the fabrication of 3D dielectric and metallic photonic nanostructures.

Model of diffusion-assisted direct laser writing by means of nanopolymerization in the presence of radical quencher

Diffusion-assisted direct laser writing (DA-DLW) by multiphoton polymerization has been recently shown to be one of the most promising methods for the high-resolution 3D nanofabrication [I. Sakellari, et al., ACS Nano 6, 2302 (2012)]. The improvement of the writing spatial resolution has been observed under certain conditions when the mobile radical quencher (polymerization inhibitor) is added to the photosensitive composition. In this work, we present a theoretical study of this method, focusing on the resolution capabilities and optimal writing parameters. The laser beam absorption in the polymerizable composition causes the localized depletion of the quencher molecules. If the quencher depletion is balanced by its diffusion from the outside of the focal volume, the quasi-stationary non-equillibrium concentration spatial profile with zero minimum can be obtained. The polymer is then effectively formed only in the domain where the quencher is depleted. The spatially-distributed quencher, in this case, ha...

High-resolution 3D woodpile structures by direct fs laser writing

A novel organic-inorganic hybrid material is presented containing a quenching moiety for improving the resolution of Direct femtosecond Laser Writing by multi-photon polymerization. By exploiting the diffusion of the quencher molecule for confining radical diffusion in the scanned area, sub-100nm resolution is achieved. 3D woodpile structures with rod spacing of 400nm are successfully fabricated. We optically characterize these woodpiles structures and we show that they exhibit well-ordered diffraction patterns and stopgaps down to near-infrared wavelengths.