The early stage formation mechanisms operating during the sublimation growth of CdTe films on CdS has been evaluated using a growth interrupt methodology for deposition under 100 Torr of N2. Key stages of the growth were identified and are discussed in terms of the processes of island nucleation, island growth/coalescence, channel formation and secondary nucleation that have been reported for other materials systems. It was demonstrated that the grain size could be manipulated by means of controlling the gas pressure in the range 2 – 200 Torr, with the grain diameter increasing with pressure linearly as D (μm) = 0.027(± 0.011) × P (Torr) + 0.90(± 0.31). For a series of solar cells made using such material, the performance parameters were seen to increase with grain size up to a plateau corresponding to grains of ∼4 μm in this case. Equivalent circuit parameters for resistive components arising from grain boundaries, and the contact to the CdTe, were measured. It is considered that grain boundary barriers in CdTe are harmful to PV performance, and that the plateau in performance occurs when the grain size is increased to the level where the contact resistance is greater than that due to grain boundaries.