Direct extraction of optical constants of organic semiconductors in ultrastrongly coupled microcavities and their application in antireflection design for polariton devices

The strongly bound Frenkel excitons in organic semiconductors enable strong or even ultrastrong exciton-photon coupling in room-temperature cavities, with the resulting polariton states typically resolved through reflectance measurements. This paper demonstrates that the distinct features of exciton and polariton modes in the reflectance spectra of strongly/ultrastrongly coupled organic microcavities can be effectively utilized to extract the optical constants and physical thickness of the embedded organic semiconductor. We investigate metal-clad microcavities based on two prototype conjugated polymers, poly[2-methoxy-5-(3,7-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) and poly(3-hexylthiophene) (P3HT), both exhibiting ultrastrong coupling characteristics. The (n,k) spectra and thickness of these polymer films are determined by fitting the normal incidence reflectance spectra of organic microcavities, using Kramers-Kronig transformation and transfer-matrix calculations with varying optical and thickness parameters. We also examine the individual effects of the main fitting parameters on the spectrum, establishing a close correlation with the underlying polariton properties. Moreover, we analyze the optical admittance at exciton and polariton modes to understand reflectance variations with different parameters, which facilitates precise control of optical properties at specific modes through cavity design. Finally, using the extracted optical constants of MDMO-PPV and P3HT, we propose optimized microcavity designs that exhibit antireflection at the lower polariton mode for potential luminescence and photodetection device applications.