The LUMINEU (Luminescent Underground Molybdenum Investigation for NEUtrino mass and nature) project envisages a high-sensitivity search for neutrinoless double beta (0 nu 2 beta) decay of Mo-100 with the help of scintillating bolometers based on zinc molybdate (ZnMoO4) crystals. One of the crucial points for the successful performance of this experiment is the development of a protocol for producing high quality large mass ZnMoO4 crystal scintillators with extremely high internal radiopurity. Here we report a significant progress in the development of large volume ZnMoO4 crystalline boules (with mass up to 1 kg) from deeply purified materials. We present and discuss the results achieved with two ZnMoO4 samples (with mass of about 0.3 kg each): one is a precursor of the LUMINEU project, while the other one was produced in the framework of LUMINEU with an improved purification / crystallization procedure. The two crystals were measured deep underground as scintillating bolometers in the EDELWEISS dilution refrigerator at the Laboratoire Souterrain de Modane (France) protected by a rock overburden corresponding to 4800 m w.e. The results indicate that both tested crystals are highly radiopure. However, the advanced LUMINEU sample shows a clear improvement with respect to the precursor, exhibiting only a trace internal contamination related with Po-210 at the level of 1 mBq/kg, while the activity of Ra-226 and Th-228 is below 0.005 mBq/kg. This demonstrates that the LUMINEU purification and crystal-growth procedures are very efficient and leads to radiopurity levels which exceedingly satisfy not only the LUMINEU goals but also the requirements of a next-generation 0 nu 2 beta experiment.