Significant improvements in the switching voltage distribution are required for the development of unipolar resistivememory devices using MnOx thin films. The Vset of the as-grown MnOx film ranged from 1 to 6.2 V, whereas the Vset of theoxygen-annealed film ranged from 2.3 to 3 V. An excess of oxygen in an MnOx film leads to an increase in Mn4+ contentat the MnOx film surface with a subsequent change in the Mn4+/Mn3+ ratio at the surface. This was attributed to the changein Mn4+/Mn3+ ratios at the MnOx surface and to grain growth. Oxygen annealing is a possible solution for improving theswitching voltage distribution of MnOx thin films. In addition, crystalline MnOx can help stabilize the Vset and Vreset distributionin memory switching in a Ti/MnOx/Pt structure. The improved uniformity was attributed not only to the change of thecrystallinity but also to the redox reaction at the interface between Ti and MnOx.

A non-volatile resistive random access memory (RRAM) device with a Cr-doped SrZrO3/SrRuO3 bottom electrode heterostructure was fabricated on SrTiO3 substrates using pulsed laser deposition. During the deposition process, the substrate temperature was 650˚C and the variable ambient oxygen pressure had a range of 50-250 mTorr. The sensitive dependences of the film structure on the processing oxygen pressure are important in controlling the bistable resistive switching of the Cr-doped SrZrO3 film. Therefore, oxygen pressure plays a crucial role in determining electrical properties and film growth characteristics such as various microstructural defects and crystallization. Inside, the microstructure and crystallinity of the Cr-doped SrZrO3 film by oxygen pressure were strong effects on the set, reset switching voltage of the Cr-doped SrZrO3. The bistable switching is related to the defects and controls their number and structure. Therefore, the relation of defects generated and resistive switching behavior by oxygen pressure change will be discussed. We found that deposition conditions and ambient oxygen pressure highly affect the switching behavior. It is suggested that the interface between the top electrode and Cr-doped SrZrO3 perovskite plays an important role in the resistive switching behavior. From I-V characteristics, a typical ON state resistance of 100-200 Ω and a typical OFF state resistance of 1-2 kΩ, were observed. These transition metal-doped perovskite thin films can be used for memory device applications due to their high ON/OFF ratio, simple device structure, and non-volatility.

One of the weak points of the Cr-doped SZO is that until now, it has only been fabricated on perovskite substrates, whereas NiO-ReRAM devices have already been deposited on Si substrates. The fabrication of RAM devices on Si substrates is important for commercialization because conventional electronics are based mainly on silicon materials. Cr-doped ReRAM will find a wide range of applications in embedded systems or conventional memory device manufacturing processes if it can be fabricated on Si substrates. For application of the commercial memory device, Cr-doped SrZrO3 perovskite thin films were deposited on a SrRuO3 bottom electrode/Si(100)substrate using pulsed laser deposition. XRD peaks corresponding to the (112), (004) and (132) planes of both the SZO and SRO were observed with the highest intensity along the (112) direction. The positions of the SZO grains matched those of the SRO grains. A well-controlled interface between the SrZrO3:Cr perovskite and the SrRuO3 bottom electrode were fabricated, so that good resistive switching behavior was observed with an on/off ratio higher than 102. A pulse test showed the switching behavior of the Pt/SrZrO3:Cr/SrRuO3 device under a pulse of 10 kHz for 104 cycles. The resistive switching memory devices made of the Cr-doped SrZrO3 thin films deposited on Si substrates are expected to be more compatible with conventional Si-based electronics.