Natural Hyperbolic Dispersion with Anisotropic Epsilon‐Near‐Zero and Epsilon‐Near‐Pole in Squaraine Molecular Film

Abstract Epsilon‐near‐zero (ENZ) optical material has been employed in a number of novel linear and nonlinear optical applications, owing to the vanishing polarization upon an incident optical wave. In a uniaxial medium possessing hyperbolic energy–momentum dispersion of optical wave, ENZ can take place at ordinary and extraordinary permittivities. Organic thin films presenting a lamellar structure have been reported to exhibit a transverse negative hyperbolic dispersion with ENZ at ordinary permittivity. Here, organic thin film with ENZ at extraordinary permittivity is demonstrated. Newly synthesized polymethine dye (i.e., squaraine indolenine triethyleneglycol molecule) self‐organizes to form a layered structure in a pristine film, and both transverse negative and positive hyperbolic dispersions are observed at visible wavelengths. Analysis of tens‐nanometer‐thick pristine film shows that both ENZ and epsilon‐near‐pole (ENP) occur at longitudinal as well as transverse component of dielectric permittivity. Optical characterization of squaraine pristine film is presented, and the importance of transverse positive hyperbolic dispersion in such monolithic thin film is discussed.