Fabrication and chemical modifications of photonic crystals produced by multiphoton lithography

This thesis is concerned with the fabrication methodology of polymeric photonic crystals operating in the visible to near infrared regions and the correlation between the chemical deposition morphologies and the resultant photonic stopband enhancements of photonic crystals. Multiphoton lithography (MPL) is a powerful approach to the fabrication of polymeric 3D micro- and nano-structures with a typical minimum feature size ~ 200 nm. The completely free-form 3D fabrication capability of MPL is very well suited to the formation of tailored photonic crystals (PCs), including structures containing well defined defects. Such structures are of considerable current interest as micro-optical devices for their filtering, stop-band, dispersion, resonator, or waveguiding properties. More specifically, the stop-band characteristics of polymer PCs can be finely controlled via nanoscale changes in rod spacings and the chemical functionalities at the polymer surface can be readily utilized to impart new optical properties. Nanoscale features as small as 65 ± 5 nm have been formed reproducibly by using 520 nm femtosecond pulsed excitation of a 4,4'-bis(di-n-butylamino)biphenyl chromophore to initiate crosslinking in a triacrylate blend. Dosimetry studies of the photoinduced polymerization were performed on chromophores with sizable two-photon absorption cross-sections at 520 and 730 nm. These studies show that sub-diffraction limited line widths are obtained in both cases with the lines written at 520 nm being smaller. Three-dimensional multiphoton lithography at 520 nm has been used to fabricate polymeric woodpile photonic crystal structures that show stop bands in the visible to near-infrared spectral region. 85 ± 4 nm features were formed using swollen gel photoresist by 730 nm excitation MPL. An index matching oil was used to induce chemical swelling of gel resists prior to MPL fabrication. When swollen matrices were subjected to multiphoton excitation, a similar excitation volume is achieved as in normal unswollen resins. However, upon deswelling of the photoresist following development a substantial reduction in feature size was obtained. PCs with high structural fidelity across 100 µm × 100 µm × 32 layers exhibited strong reflectivity (>60% compared to a gold mirror) in the near infrared region. The positions of the stop-bands were tuned by varying the swelling time, the exposure power (which modifies the feature sizes), and the layer spacing between rods. Silver coatings have been applied to PCs with a range of coverage densities and thicknesses using electroless deposition. Sparse coatings resulted in enhanced reflectivity for the stop band located at ~5 µm, suggesting improved interface reflectivity inside the photonic crystal due to the Ag coating. Thick coatings resulted in plasmonic bandgap behavior with broadband reflectivity enhancement and PC lattice related bandedge at 1.75 µm. Conformal titania coatings were grown onto the PCs via a surface sol-gel method. Uniform and smooth titania coatings were achieved, resulting in systematically red-shifted stopbands from their initial positions with increasing thicknesses, corresponding to the increased effective refractive index of the PC. High quality titania shell structures with modest stopbands were obtained after polymer removal. Gold replica structures were obtained by electroless deposition on the silica cell walls of naturally occurring diatoms and the subsequent silica removal. The micron-scaled periodic hole lattice originated from the diatom resulted in surface plasmon interferences when excited by infrared frequencies. The hole patterns were characterized and compared with hexagonal hole arrays fabricated by focused ion beam etching of similarly gold plated substrate. Modeling of the hole arrays concluded that while diatom replicas lack long-ranged periodicity, the local hole to hole spacings were sufficient to generate enhanced transmission of 13% at 4.2 µm. The work presented herein is a step towards the development of PCs with new optical and chemical functionalities. The ability to rapidly prototype polymeric PCs of various lattice parameters using MPL combined with facile coating chemistries to create structures with the desired optical properties offers a powerful means to produce tailored high performance photonic crystal devices.Ph