Enabling High Precision Gradient Index Control in Subsurface Multiphoton Lithography.

Multiphoton lithography inside a mesoporous host can create optical components with continuously tunable refractive indices in three-dimensional (3D) space. However, the process is very sensitive at exposure doses near the photoresist threshold, leading previous work to reliably achieve only a fraction of the available refractive index range for a given material system. Here, we present a method for greatly enhancing the uniformity of the subsurface micro-optics, increasing the reliable index range from 0.12 (in prior work) to 0.37 and decreasing the standard deviation (SD) at threshold from 0.13 to 0.0021. Three modifications to the previous method enable higher uniformity in all three spatial dimensions: (1) calibrating the planar write field of mirror galvanometers using a spatially varying optical transmission function which corrects for large-scale optical aberrations; (2) periodically relocating the piezoelectrically driven stage, termed piezo-galvo dithering, to reduce small-scale errors in writing; and (3) enforcing a constant time between each lateral cross section to reduce variation across all writing depths. With this new method, accurate fabrication of optics of any index between n = 1.20 and 1.57 (SD < 0.012 across the full range) was achieved inside a volume of porous silica. We demonstrate the importance of this increased accuracy and precision by fabricating and characterizing calibrated two-dimensional (2D) line gratings and flat gradient index lenses with significantly better performance than the corresponding control devices. As a visual representation, the University of Illinois logo made with 2D line gratings shows significant improvement in its color uniformity across its width.

Absorbance amplification using chromophore-nanoplasmon coupling for ultrasensitive protein quantification.

A plasmonic nanoscale Lycurgus cup array (nanoLCA), via near-field interaction with chromophores in commercial colorimetric biochemical assays, can drastically enhance assay sensitivity by over 2 orders of magnitude. A 96-microwell plate modified by placing the plasmonic nanoLCA on the well-bottom was used with the commercial Bradford protein quantification assay. Plasmons on the nanoLCA serve as an energy donor to matched resonance chromophores, and the near-field plasmonic energy coupling effect results in an increase in absorbance value at the plasmonic resonance wavelength. Even with a 5.1-fold reduced sample volume, a limit of detection enhancement factor of 200 is accomplished using the nanoLCA compared to using the conventional Bradford assay without plasmon aid. The nanoLCA-microplate sensing platform is readily scalable to 384- or 1536-microwell plates, which further reduces the sensing volume and boosts detection throughput with the enhanced sensitivity.