The authors have fabricated p-on-n LWIR HgCdTe diodes by extrinsically doping a double-layer heterostructure grown by metalorganic chemical vapour deposition (MOCVD) using the interdiffused multilayer process (IMP) on GaAs substrates. The p-side of the junction was obtained by a fast As diffusion, from an ion-implanted source, ahead of the heterointerface when the annealing was performed at very low partial pressure of Hg. Examples of photodiodes fabricated by this process are given. Thus, for devices processed by As implant/diffusion, an R₀A of 24.2 Omega cm² for a cut-off wavelength of 11.7 mu m at 77 K and a quantum efficiency of 51% were obtained for a mesa unpassivated structure, and an R₀A of 91 Omega cm² for a cut-off wavelength of 10.3 at 77 K and a quantum efficiency of 50% were obtained for a planar structure. At 77 K the transport mechanisms limiting the device performance near zero bias have appeared to be thermal processes (ideality factor n between 1 and 2). However, other mechanisms evident in reverse bias such as shunt and tunnelling, may also operate.