Enhanced Two-Photon Photochromism in Metasurface Perfect Absorbers.

Light switchable materials are essential to optoelectronic applications in photovoltaics, memories, sensors, and communications. Natural switchable materials suffer from weak absorption and slow response times, preventing their use in low-power, ultrafast applications. Integrating light switchable materials with metasurface perfect absorbers offers an innovative route to achieving desirable features for nanophotonic devices, such as directional emission, low-power and broadband operation, high radiative quantum efficiency, and large spontaneous emission rates. Here we show an enhanced two-photon photochromism based on a metasurface perfect absorber: film-coupled colloidal silver nanocubes. The photochromic molecules, spiropyrans, are sandwiched between the silver nanocubes and the gold substrate. With nearly 100% absorption and an accompanying large field enhancement in the molecular junction, the transformation of spiropyrans to merocyanines is observed under excitation with 792 nm laser light. Fluorescence lifetime measurements on the merocyanine form reveal that large Purcell enhancement in the film-coupled nanocubes leads to large enhancements of the spontaneous emission rate and a high quantum efficiency. An averaged incident power as low as 10 μW is enough to initiate the two-photon isomerization of spiropyran in the film-coupled nanocubes, and a power of 100nW is able to excite the merocyanines to emit fluorescence. The power consumption is orders of magnitude lower than bare spiropyran thin films on silicon and gold, which is highly desirable for the writing and reading processes relevant to optical data storage. By sweeping the plasmonic resonance of the film-coupled nanocubes, wavelength specificity is demonstrated, which opens up new possibilities for minimizing the cross talk between adjacent bits in nanophotonic devices.