Pyroelectric and electrocaloric effects in ferroelectric silicon-doped hafnium oxide thin films
The emergent ferroelectricity in HfO 2 -based systems has attracted significant attention as this simple binary high- k dielectric now offers the possibility of nonvolatile function. Here we employ zero-field and field-dependent pyroelectricity to show that thin films of silicon-doped HfO 2 do exhibit a broken-inversion symmetry and are indeed ferroelectric. In addition, the pyroelectric response is found to exhibit a wake-up behavior akin to the wake-up phenomenon observed in the ferroelectric polarization with electric-field cycling. Using polarization-electric field hysteresis measurements, this wake-up phenomenon is attributed to the presence of defect dipoles which explains the measured pyroelectric response. Finally, direct electrocaloric measurements are performed on these silicon-doped HfO 2 thin films, revealing an electrocaloric coefficient ~ 4 times larger in magnitude than that expected for the measured pyroelectric coefficient. This enhancement is explained using the plausible role played by defect dipoles that contribute to additional configurational or dipolar entropy.