Nitrogen (N) doped ZnSe homoepitaxial films and bulk single crystals doped with phosphorus (P), antimony (Sb) and bismuth (Bi), have been grown by metal-organic chemical vapor deposition (MOCVD) and Bridgman method, respectively. By examining photoluminescence (PL) spectra at low temperature, it is found that group Va elements act as both shallow acceptor and deep donor. To enhance the net acceptor concentration, ZnSe:Va specimens are annealed at different temperatures. The experimental results show that doped Va elements except P are activated remarkably. The C-V measurements show that the highest net acceptor concentration is 6.7 x 10(17) cm(-3) in ZnSe:N. Furthermore, the ionization energies of Va elements as acceptors and deep donor complexes are estimated. (c) 2006 Elsevier B.V. All rights reserved.