Metallo-dielectric photonic crystals (MDPCs) can exhibit intriguing and potentially useful optical properties, including
ultra-wide photonic bandgaps, engineered thermal emission, and negative refractive index. But access to such materials
has been limited by the lack of suitable methods for their preparation. We have developed a route to three-dimensional
(3D) MDPCs that involves fabricating a polymeric pre-form by multi-photon direct laser writing and then conformally
depositing metal onto the pre-form by electroless metallization. We use the approach to prepare silver- and copper-plated
"woodpile" PCs having face-centered tetragonal symmetry and unit-cell period of several micrometers. The
resulting 3D metallized structures exhibit mid-infrared reflectance that is consistent with theory and experimental
observations obtained for MDPCs prepared by other routes. These data indicate that multi-photon direct laser writing
coupled with electroless metallization is a viable route to complex 3D MDPCs of many symmetries and basis sets and
provides a path for integrating such structures with other micron-scale optical elements.
Interest in three-dimensional (3D) metallo-dielectric photonic crystals (MDPCs) has grown considerably given their
potential applications in optics and photonics. MDPCs can exhibit intriguing and potentially useful optical properties,
including ultra-wide photonic bandgaps, engineered thermal emission, and negative refractive index. Yet experimental
studies of such materials remain few because of the difficulties associated with fabricating 3D micron- and sub-micron-scale
metallic structures. We report a route to MDPCs based on metallization of a 3D polymeric photonic crystal (PC)
fabricated by multi-photon microfabrication (MPM). Polymeric PCs having face-centered tetragonal symmetry and
micrometer-scale periodicity were created using a cross-linkable acrylate or epoxide pre-polymer. The resulting PCs
were metallized by electroless deposition of silver or copper. Analysis of the metallized structures in cross-section by
scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy shows that silver deposited conformally
onto the entire micro-porous lattice. The dielectric and metallized PCs were characterized by Fourier transform infrared
(FTIR) spectroscopy. The polymer photonic crystals exhibit a stop band with strong reflectance near 4 to 6 microns,
depending upon the lattice period. In contrast, FTIR spectra of the metallized PCs show widened stop bands of nearly
6 microns and greater and maximum reflectance exceeding 90%. The appreciable broadening of the stop band due to the
presence of the deposited metal is a result consistent with previously reported theoretical and experimental data for all-metallic
3D PCs. Thus, the approach reported here appears suitable for fabricating 3D MDPCs of many symmetries and
basis sets and provides a path for integrating such structures with other micron-scale optical elements.
Interest in three-dimensional (3D) metal photonic crystals (MPCs) has grown considerably given their potential applications in optics and photonics. Yet, experimental studies of such materials remain few because of the difficulties associated with fabricating 3D micron- and sub-micron-scale metallic structures. We report a route to MPCs based on metallization of 3D polymeric photonic crystals fabricated by multi-photon direct laser writing. Polymeric photonic crystals (PCs) having simple-cubic symmetry with periodicities varying from 1.6 to 3.2 microns were created using a cross-linkable acrylate pre-polymer. The resulting dielectric PCs were metallized by electroless deposition of silver. Analysis of the metallized structures in cross-section by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy shows that silver deposited conformally onto the entire micro-porous lattice. The dielectric and metallized PCs were characterized by Fourier transform infrared (FTIR) spectroscopy in the (001) direction. The polymer photonic crystals exhibit a stop band resulting in circa 60% reflectance centered at 3.2 to 6.4 microns, depending upon the lattice period, with a full-width at half-maximum (FWHM) of 500 nm. Interestingly, FTIR spectra of the metallized PCs show widened stop bands of nearly 6 microns FWHM, while the center wavelengths were red shifted and ranged from 6 to 7 microns. The appreciable broadening of the stop band due to the presence of the deposited silver is a result consistent with previously reported theoretical and experimental data for all-metallic 3D PCs. Thus, the approach described here appears suitable for fabricating 3D MPCs of many symmetries and basis sets and provides a path for integrating such structures with other micron-scale optical elements.
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