The crystalline structure and electrical response of La-doped HfO₂-ZrO₂ thin films of which processing temperature did not exceed 400 °C were examined, where the La-doping concentration was varied from zero to ≈2 mol. %. The film structure and associated properties were found to vary sensitively with the minute variation in the La-concentration, where the ferroelectric response at low La-concentration (<≈1 mol. %) gradually became antiferroelectric-like for La-concentration >≈1 mol. %, which was accompanied by a significant increase in dielectric permittivity. La-doping was found to be very effective in inhibiting the monoclinic phase formation and in decreasing the leakage current. Notably, the high coercive field, which was one of the most significant problems in this material system, could be decreased by ∼35% at the most promising La-concentration of 0.7 mol. %. As a result, a highly promising field cycling endurance up to 10¹¹ cycles could be secured while maintaining a high remnant polarization value (≥25 μC/cm²). This is one of the best results in this field of the authors' knowledge.

We report the possibility of employment of low temperature (≤330 °C) plasma-enhanced atomic layer deposition for the formation of both electrodes and hafnium-oxide based ferroelectric in the metal-insulator-metal structures. The structural and ferroelectric properties of La doped HfO₂-based layers and its evolution with the change of both La content (2.1, 3.7 and 5.8 at. %) and the temperature of the rapid thermal processing (550–750 °C) were investigated in detail. Ferroelectric properties emerged only for 2.1 and 3.7 at. % of La due to the structural changes caused by the given doping levels. Ferroelectric properties were also found to depend strongly on annealing temperature, with the most robust ferroelectric response for lowest La concentration and intermediate 650 °C annealing temperature. The long term wake-up effect and such promising endurance characteristics as 3 × 10⁸ switches by bipolar voltage cycles with 30 μs duration and ± 3 MV/cm amplitude without any decrease of remnant polarization value were demonstrated.

Recently proposed novel neural network hardware designs imply the use of memristors as electronic synapses in 3D cross-bar architecture. Atomic layer deposition (ALD) is the most feasible technique to fabricate such arrays. In this work, we present the results of the detailed investigation of the gradual resistive switching (memristive) effect in nanometer thick fully ALD grown TiN/HfO₂/TiN stacks. The modelling of the I-V curves confirms interface limited trap-assisted-tunneling mechanism along the oxygen vacancies in HfO₂ in all conduction states. The resistivity of the stack is found to critically depend upon the distance from the interface to the first trap in HfO₂. The memristive properties of ALD grown TiN/HfO₂/TiN devices are correlated with the demonstrated neuromorphic functionalities, such as long-term potentiation/depression and spike-timing dependent plasticity, thus indicating their potential as electronic synapses in neuromorphic hardware.