Revealing Antiferroelectric Switching and Ferroelectric Wakeup in Hafnia by Advanced Piezoresponse Force Microscopy

Hafnium oxide (HfO2)-based ferroelectrics offer remarkable promise for memory and logic devices in view of their compatibility with traditional silicon complementary metal oxide semiconductor (CMOS) technology, high switchable polarization, good endurance, and thickness scalability. These factors have led to a steep rise in the level of research on HfO2 over the past number of years. While measurements on capacitors are promising for understanding macroscopic effects, many open questions regarding the emergence of ferroelectricity and electric field cycling behaviors remain. Continued progress requires information regarding the nanoscale ferroelectric behaviors on the bare surface (i.e., without encapsulation), which is notably absent. To overcome this barrier, we have applied complementary modes of piezoresponse force microscopy with the goal of directly and quantitatively sensing nanoscale ferroelectric behaviors in bare HfO2 thin films. Our results on 8 nm Si-doped HfO2 reveal nanoscale domains of local remnant polarization states exhibiting a weak piezoelectric coupling (deff) in the range 0.6-1.5 pm/V. While we observed localized enhancement of deff during progressive stressing of the bare HfO2 thin film, we did not detect stable polarization switching which is a prerequisite of ferroelectric switching. This result could be explained using polarization switching spectroscopy which revealed antiferroelectric-like switching in the form of pinched hysteresis loops as well as increasing remnant response with repeated cycling. As such, our results offer a promising route for material scientists who want to explore the nanoscale origins of antiferroelectricity and ferroelectric wakeup in HfO2.