Stoke's shift and quantum efficiency enhancement in fluorescent coumarin aldehyde (HMCA) dye-conjugated chitosan matrix for optoelectronic applications

Abstract

A greenish-yellow emissive fluorescent coumarin aldehyde conjugated chitosan matrix was prepared by performing a Schiff base reaction between 7-hydroxy-4-methyl-2-oxo-2H-chromene-8-carbaldehyde (HMCA) and chitosan. The newly formed imine linkage was confirmed by the appearance of an absorption band at 1641 cm−1 in the IR spectrum and also supported by the solid-state 13C-NMR with cross polarisation magic angle spinning (CPMAS) method. The molecular weight of the HMCA-conjugated chitosan matrix was augmented with an increase in the HMCA concentration. The SEM images unveiled crystallite aggregates in the chitosan matrix and the improved crystallinity was witnessed in the PXRD result. The chemically conjugated chitosan film unveiled a larger Stoke's shift value of 183–224 nm which was just 50–130 nm in pure HMCA. The conjugate material could overcome the self-absorption issue associated with the coumarin aldehyde. The coumarin aldehyde exhibited dual emission at 390 nm and 440 nm but it was shifted to 520 nm with single emission upon reaction with chitosan. The observed redshift could be assigned for the formation of static excimer that resulted from the chitosan backbone containing pendant chromophore (coumarin dye) which could interact with another neighbouring chromophoric group of the same chain or different chain creating a ground-state stable dimer. The emission of conjugate material shifted from blue to greenish yellow region with a higher quantum yield of 30.21 % compared to 8.57 % of HMCA alone. The calculated indirect band gap of 2.25–2.34 and the optimum refractive index suggested the potential optoelectronic applications of HMCA-conjugated chitosan as an OLED Material.