Ferroelectricity in Ultrathin HfO₂-Based Films by Nanosecond Laser Annealing

Nonvolatile memory devices based on ferroelectric Hf_xZr_1-xO₂ (HZO) show great promise for back-end integrable storage and for neuromorphic accelerators, but their adoption is held back by the inability to scale down the HZO thickness without violating the strict thermal restrictions of the Si CMOS back end of line. In this work, we overcome this challenge and demonstrate the use of nanosecond pulsed laser annealing (NLA) to locally crystallize areas of an ultrathin (3.6 nm) HZO film into the ferroelectric orthorhombic phase. Meanwhile, the heat induced by the pulsed laser is confined to the layers above the Si, allowing for back-end compatible integration. We use a combination of electrical characterization, nanofocused scanning X-ray diffraction (nano-XRD), and synchrotron X-ray photoelectron spectroscopy (SXPS) to gain a comprehensive view of the change in material and interface properties by systematically varying both laser energy and the number of laser pulses on the same sample. We find that NLA can provide remanent polarization up to 2P_r= 11.6 μC/cm² in 3.6 nm HZO, albeit with a significant wake-up effect. The improved TiN/HZO interface observed by XPS explains why device endurance goes beyond 10⁷ cycles, whereas an identical film processed by rapid thermal processing (RTP) breaks already after 10⁶ cycles. All in all, NLA provides a promising approach to scale down the ferroelectric oxide thickness for emerging HZO ferroelectric devices, which is key for their integration in scaled process nodes.