In this work, a novel customized shadowed off-axis deposition set-up is used to perform an original study of Ge nanoparticles (NPs) formation in an inert Ar gas atmosphere by pulsed laser deposition at room temperature varying systematically the background Ar gas pressure (Pbase(Ar)), target–substrate distance (d) and laser repetition rate (f). The influence of these parameters on the final NPs size distributions is investigated and a fairly uniform droplets-free and non-agglomerated NPs distribution with average height 〈h〉=2.8±0.6nm is obtained for optimized experimental conditions (Pbase(Ar)=1mbar; d=3cm; f=10Hz) with a fine control in the NPs density (from 3.2×109cm−2 to 1.1×1011cm−2). The crystalline quality of as-deposited NPs investigations demonstrate a strong dependence with the Ar gas pressure and a crystalline to amorphous phase volume fraction χc>50% is found for Pbase(Ar)=2mbar. The NPs functionality for charge trapping applications has been successfully demonstrated by capacitance–voltage (C–V) electrical measurements.