Nanofabrication of Bulk Diffraction Nanogratings via Direct Ultrashort-Pulse Laser Micro-Inscription in Elastomers and Heat-Shrinkable Polymers.

Optical-range bulk diffraction nanogratings were fabricated via challenging direct inscription by ultrashort (femtosecond, fs) laser pulses inside heat-shrinkable polymers (thermoplastics) and VHB 4905 elastomer. The inscribed bulk material modifications do not emerge on the polymer surface, being visualized inside the materials by 3D-scanning confocal photoluminescence/Raman microspectroscopy and by the multi-micron penetrating 30-keV electron beam in scanning electron microscopy. The laser-inscribed bulk gratings have multi-micron periods in the pre-stretched material after the second laser inscription step, with their periods continuously reduced down to 350 nm on the third fabrication step, using thermal shrinkage for thermoplastics and elastic properties for elastomers. This three-step process allows facile laser micro-inscription of diffraction patterns and their following controlled scaling down as a whole pattern to pre-determined dimensions. In elastomers, utilizing the initial stress anisotropy, the post-radiation elastic shrinkage along the given axes could be precisely controlled until the 28-nJ threshold fs-laser pulse energy, where elastomer deformation ability is dramatically reduced, producing wrinkled patterns. In thermoplastics, the fs-laser inscription does not affect their heat-shrinkage deformation up to the carbonization threshold. The measured diffraction efficiency of the inscribed gratings increases during the elastic shrinkage for the elastomers and slightly decreases for the thermoplastics. High 10% diffraction efficiency was demonstrated for the VHB 4905 elastomer at the 350 nm grating period. No significant molecular-level structural modifications were observed by Raman micro-spectroscopy in the inscribed bulk gratings in the polymers. This novel few-step method paves the way for facile and robust ultrashort-pulse laser inscription of bulk functional optical elements in polymeric materials for diffraction, holographic and virtual reality devices.