(Digital Presentation) CeOx Capping for Ferroelectric Y:HfO2 Films

Abstract

In recent years, HfO2 has been paid a lot of attention as a ferroelectric material due to its excellent scalability and complementary-metal-oxide-semiconductor (CMOS) process compatibility [1]. Some of the issues of ferroelectric HfO2 are wake-up and fatigue effect, increase and decrease of remanent polarization (P r) along with switching cycles, and low endurance. Generally, these phenomena are understood as a result of the increase and redistribution of oxygen vacancies (VO) in HfO2 films [2]. By the way, it is reported that CeOx can release and absorb oxygen from adjacent oxides [3]. In this study, we propose the stacking structure of CeOx and ferroelectric HfO2 to improve endurance and investigate electric properties and voltage application sequence to suppress the fatigue effect.5 mol% Y-doped HfO2 (Y:HfO2) and CeOx capping layers of metal-ferroelectric-metal (MFM) capacitors were deposited by atomic-layer-deposition (ALD) with W bottom and top electrodes by sputtering. Post metallization annealing (PMA) was performed at 450 and 500oC for the various duration. Figure 1 shows hysteresis loops of the capacitors with and without CeOx capping annealed at 450oC for 20 minutes. Large hysteresis on CeOx capping is observed even same annealing temperature and duration. Enhancement of transformation to ferroelectric phase can be explained as tensile stress to Y:HfO2 due to the difference of coefficient of thermal expansion (CTE) between CeOx and Y:HfO2. Variation of switching polarization (P SW), the difference between positive and negative P r, as a function of the number of switching cycles is also investigated and shown in figure 2. Both capacitors are annealed at 500oC for 100 minutes to crystallize. In the case of without CeOx capping, continuous wake-up effect and breakdown over 3×107 times switching are observed. On the other hand, the capacitor with CeOx capping shows a slight wake-up effect and fatigue after 106 times switching, additionally, endurance is improved to 3×109 times switching. The reason why fatigue and prolonging endurance occur is suspected that oxygen ions in the CeOx layer pin polarization domains and compensate VO in Y:HfO2. To suppress fatigue, we propose the recovery process by positive DC voltage application to top electrodes. In figure 3, hysteresis loops of the capacitor with CeOx capping before and after recovery voltage application. One can observe the larger hysteresis after recovery.This work was supported by JST-COI (JPMJCE1309). One of the authors, Kazuto Mizutani, was supported by The FUTABA Foundation.[1] T. S. Boscke, et al., Appl. Phys. Lett., 99, 102903 (2011). [2] M. Pesic, et al., Adv. Funct. Mater., 26, pp. 4601–4612 (2016). [3] M. Mamatrishat, et al., Vacuum, 86, pp. 1513-1513 (2012). Figure 1