High Refractive Index Polymer Thin Films by Charge-Transfer Complexation

High refractive index polymers are essential in next-generation flexible optical and optoelectronic devices. This paper describes a simple synthetic method to prepare polymeric optical coatings possessing high refractive indexes. Poly(4-vinylpyridine) (P4VP) thin films prepared using initiated chemical vapor deposition are exposed to highly polarizable halogen molecules to form stable charge-transfer complexes: P4VP-IX (X = I, Br, and Cl). Fourier transform infrared spectroscopy was used to confirm the formation of charge-transfer complexes. Characterized by spectroscopic ellipsometry, the maximum refractive index of 2.08 at 587.6 nm is obtained for P4VP-I₂. For P4VP-IBr and P4VP-ICl, the maximum refractive indexes are 1.849 and 1.774, respectively. By controlling the concentration of charge-transfer complexes, either through the halogen incorporation step or polymer composition through copolymerization with ethylene glycol dimethacrylate, the refractive indexes of the polymer thin films can be precisely controlled. The feasibility of P4VP-IX materials as optical coatings is also explored. The refractive index and thickness uniformity of a P4VP-I₂ film over a 10 mm diameter circular area were characterized, showing standard deviations of 0.0769 and 1.91%, respectively.