The authors demonstrate a unique low cost process to print 2D, submicron size, and high refractive index nanopillars using a direct colloidal-photolithography process. A well collimated i-line source emitting at 365 nm wavelength illuminates a mono layer of silica microspheres of 1 μm diameter deposited on a photosensitive TiO2-based sol-gel layer. No etching process is needed since this layer is directly UV photo patternable like a negative photoresist. Furthermore, this thin layer offers interesting optical properties (high refractive index and optical transparency) and good mechanical and chemical stability and thus can be directly used as a functional microstructure (for PV or sensor applications, for example). The paper describes the modeling of the electric field distribution below the spheres during the illumination process, the photochemistry of the TiO2 sol-gel layer process, and preliminary results of TiO2 nanopillars of around 200 nm in diameter fabricated on a three-inch substrate.
In this work, direct irradiation by a Ti:Sapphire (100 fs) femtosecond laser beam at third harmonic (266 nm), with a moderate repetition rate (50 and 1000 Hz), was used to create regular periodic nanostructures upon polystyrene (PS) thin films. Typical Low Spatial Frequency LIPSSs (LSFLs) were obtained for 50 Hz, as well as for 1 kHz, in cases of one spot zone, and also using a line scanning irradiation. Laser beam fluence, repetition rate, number of pulses (or irradiation time), and scan velocity were optimized to lead to the formation of various periodic nanostructures. It was found that the surface morphology of PS strongly depends on the accumulation of a high number of pulses (103 to 107 pulses) at low energy (1 to 20 µJ/pulse). Additionally, heating the substrate from room temperature up to 97 °C during the laser irradiation modified the ripples’ morphology, particularly their amplitude enhancement from 12 nm (RT) to 20 nm. Scanning electron microscopy and atomic force microscopy were used to image the morphological features of the surface structures. Laser-beam scanning at a chosen speed allowed for the generation of well-resolved ripples on the polymer film and homogeneity over a large area.
This paper presents substantial improvements of the colloidal photolithography technique (also called microsphere lithography) with the goal of better controlling the geometry of the fabricated nano-scale structures—in this case, hexagonally arranged nanopillars—printed in a layer of directly photopatternable sol-gel TiO2. Firstly, to increase the achievable structure height the photosensitive layer underneath the microspheres is deposited on a reflective layer instead of the usual transparent substrate. Secondly, an increased width of the pillars is achieved by tilting the incident wave and using multiple exposures or substrate rotation, additionally allowing to better control the shape of the pillar’s cross section. The theoretical analysis is carried out by rigorous modelling of the photonics nanojet underneath the microspheres and by optimizing the experimental conditions. Aspect ratios (structure height/lateral structure size) greater than 2 are predicted and demonstrated experimentally for structure dimensions in the sub micrometer range, as well as line/space ratios (lateral pillar size/distance between pillars) greater than 1. These nanostructures could lead for example to materials exhibiting efficient light trapping in the visible and near-infrared range, as well as improved hydrophobic or photocatalytic properties for numerous applications in environmental and photovoltaic systems.
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