In-situ functionalization of nonpolar a-plane gallium nitride (GaN) surface was achieved by adding cysteamine to phosphoric acid, aiming to modulate its optical properties. The emission properties and oxide formation were explored through surface characterization with atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL), and water contact angle. Nonpolar a-plane bulk GaN sample sliced from a GaN boule and nonpolar a-plane GaN thin layer heteroepitaxially grown on r-plane sapphire were used to elucidate the effects of in-situ functionalization of identical surface orientation of GaN crystals with different defect ensembles. The addition of cysteamine to the phosphoric acid solution was found to result in: (i) increased surface roughness, (ii) no change to hydrophobicity, (iii) decreased oxygen content at high solution temperatures and increased gallium and nitrogen content versus phosphoric acid solutions at similar temperatures without cysteamine. The in-situ functionalization resulted in enhanced PL intensity from the nonpolar bulk GaN, while the PL intensity from the nonpolar heteroepitaxially grown GaN layer on sapphire was significantly reduced. The opposite PL modulation was explained by the effects of different defects present in the two samples on the nonradiative recombination. (C) 2014 Elsevier B. V. All rights reserved.