  The structural symmetry of solids plays an important role in defining their
linear and nonlinear optical properties. The quest for versatile,
cost-effective, large-scale, and defect-free approaches and materials platforms
for tailoring structural and optical properties on demand has been underway for
decades. We experimentally demonstrate a bottom-up self-assembly-based organic
engineered material comprised of synthesized molecules with large dipole
moments that are crystallized into a spherulite structure. The molecules align
in an azimuthal direction, resulting in a vortex polarity with spontaneously
broken symmetry leading to strong optical anisotropy and nonlinear optical
responses. These unique polarization properties of the judiciously designed
organic spherulite combined with the symmetry of structured optical beams
enable a plethora of new linear and nonlinear light-matter interactions,
including the generation of optical vortex beams with complex spin states and
on-demand topological charges at the fundamental, doubled, and tripled
frequencies. The results of this work are likely to enable numerous
applications in areas such as high-dimensional quantum information processing,
with large capacity and high security. The demonstrated spherulite crystals
facilitate stand-alone micro-scale devices that rely on the unique micro-scale
spontaneous vortex polarity that is likely to enable future applications for
high-dimensional quantum information processing, spatiotemporal optical
vortices, and a novel platform for optical manipulation and trapping.
