Taking the most classic resistive switching mechanism (ionic effect) as an example, it can be divided into valence change memory
92 and electrochemical metallization memory
93, which correspond to the mechanism of oxygen anions (dielectric layer) and active metal ions (electrodes) directed moving under an electric field to eventually form conductive filaments (CFs), respectively, as shown in
Fig. 3a. The fundamental
I-
V curve is depicted, as in
Fig. 3b. In the off state, as the positive voltage increases, the conductance changes from a high-resistance state (HRS) to a low-resistance state (LRS); in the on state, as the negative voltage decreases, the conductance changes back from a LRS to a HRS, and the read voltage always remains at a low positive voltage
94. However, this ion-conduction-based method will bring some problems, for example, continuous write-erase operations will cause durability failures due to the destructive nature of the programming method, and the conductance state after programming will drift over time. Therefore, even if the on/off ratio of device is very large, there are only a few stable and available conductance states that can be reached. Non-volatile memristors are mainly used to simulate synaptic plasticity by adjusting their multi-level conductance states in neural networks
37,95,96. which puts higher requirements on the linearity, symmetry, durability, and retention of the memristor working curve. To meet these requirements, researchers are keep optimizing relevant performance through doping, interlayering, annealing, and other methods. Interlayering can effectively improve the linearity and symmetry of memristor conductance curves. Zongwei Wang et al. inserted a SiO
2 layer that restricts oxygen-ion diffusion at the TiN/TaO
x interface (Scanning Transmission Electron Microscopy (STEM) image is shown in
Fig. 4a) to achieve uniform conductance modulation. This method can effectively suppress the growth/dissolution rate of CFs in memristors, thereby achieving more uniform conductance modulation, increasing linearity and symmetry (
Fig. 4b-c)
97. Lei Wu et al. found that the resistance evolution of Al-doped HfO
2 devices is milder than that of undoped Al (
Fig. 4d) and that multi-value storage of devices can be achieved by changing the limiting current or using pulse sequences and that the retention time of the multi-conductance state of the device exceeds 10
4 s at 85 °C
98. Woo Sik Choi et al. inserted Al
2O
3 into InGaZnO memristors, achieving higher durability and more stable transient characteristics. As shown in
Fig. 4e, in 500 scanning cycles, compared with the instability of the S
1 (without Al
2O
3 intercalation) conductance state, the conductance fluctuation of S
2 (with Al
2O
3 intercalation) is much smaller. Moreover, the high resistance of Al
2O
3 can suppress thermal fluctuations, and S
2 shows more stable transient characteristics and smaller resistance state changes (
Fig. 4f)
99. Interlayering combined with doping can further improve the durability and retention of memristor conductance. Yun-Lai Zhu et al. used the method of interface doping (combination of doping and interlayering) to improve the performance of TiN/HfO
2/Pt memristors. They prepared two optimized devices with different insertion configurations, namely TiN/HfO
2/HfO
2:Al/Pt and TiN/HfO
2:Al/HfO
2/Pt. The former device showed improved durability and retention, whereas the latter showed a decline in performance. This is because different insertion positions lead to different CF formation/breakdown mechanisms; therefore, it is necessary to pay attention to the impact on CF formation/breakdown in the meantime
101. Annealing treatment in inert atmosphere can improve the uniformity of ion or vacancy distribution in the device, further optimizing and stabilizing the performance of memristors. Yongyue Xiao et al. studied the effect of N
2 environment annealing treatment on the performance of Pt/HfO
2/BiFeO
3/HfO
2/TiN structure memristors. After N
2 annealing, the uniformity of the memristor (
Fig. 4g), and the pulse linearity were improved (
Fig. 4i). Furthermore, the durability was increased by 10
3 times (
Fig. 4h). As we know, the conductance regulation of oxide-type memristors can be attributed to the migration of oxygen vacancies to form CF. Annealing in N
2 produces more oxygen vacancies in the oxide, therefore, resulting in a better control to the conductance of memristors
100.