The performances of GaAs-based Gunn diodes with a notch-δ-doped structure have been studied in this work. The δ-doped effect has been analysed using Monte Carlo modelling in terms of temporal evolution of current density, electric field profile, electron energy, mean velocity, and occupancy in Γ and higher valleys. The presence of a δ-doped layer after the notch caused a significant increase in the harmonic current amplitude of the device, where the growth of high field domain can be attributed to a slow electron track due to the well-known Gunn effect and an additional fast electron track which appears over a short time window when the domain is reaching the anode. An optimised GaAs notch-δ-doped structure with 700 nm device length including 100 nm notch and 5 nm δ-doped layer can generate signals at fundamental frequency of 262 GHz with a current harmonic amplitude of 29.4×107 A/m2, which is almost twice of that without δ-doped layer. Its second and third harmonic signals are found substantial reaching into the THz range of 512 GHz and 769 GHz.