This paper presents results of experimental and theoretical research on antimonide‐ based thermophotovoltaic (TPV) materials and cells. The topics discussed include: growth of large diameter ternary GaInSb bulk crystals, substrate preparation, diffused junction processes, cell fabrication and characterization, and, cell modeling. Ternary GaInSb boules up to 2 inches in diameter have been grown using the vertical Bridgman technique with a novel self solute feeding technique. A single step diffusion process followed by precise etching of the diffused layer has been developed to obtain a diffusion profile appropriate for high efficiency, p‐n junction GaSb and GaInSb thermophotovoltaic cells. The optimum junction depth to obtain the highest quantum efficiency and open circuit voltage has been identified based on diffusion lengths (or minority carrier lifetimes), carrier mobility and experimental diffused impurity profiles. Theoretical assessment of the performance of ternary (GaInSb) and binary (GaSb) cells fabricated by Zn diffusion in bulk substrates has been performed using PC‐1D one‐dimensional computer simulations. Several factors affecting the cell performances such as the effects of emitter doping profile, emitter thickness and recombination mechanisms (Auger, radiative and Shockley‐Read‐Hall), the advantages of surface passivation and the impact of dark current due to the metallic grid will be discussed. The conditions needed for diffused junction cells on ternary and binary substrates to achieve similar performance to the epitaxially grown lattice‐ matched quaternary cells are identified. © 2003 American Institute of Physics