Hybrid Dry and Wet Etching of LiNbO₃ Domain-Wall Memory Devices with 90° Etching Angles and Excellent Electrical...

Ferroelectric domain walls, agile nanoscale interfaces of polar order, can be selectively controlled by electric fields for their position, conformation, and function, which is ultimately the key to realizing novel low-energy memory and computing structures. LiNbO₃ single-crystal domain wall memory has the advantages of high operational speed, high integration density, and virtually unlimited endurance cycles, appearing as a good solution for the next generation of highly miniaturized low-energy memories. However, the etching process poses significant challenges in the nanofabrication and high-density integration of LiNbO₃ domain-wall memories. Here, we employed a hybrid etching technique to achieve smooth sidewalls with a 90° inclined angle, leading to a 24% reduction in the coercive field and a 2.5-fold increase in the linear domain wall current density with a retention time of more than 10⁶ seconds and endurance of over 10⁵ writing cycles. Combined with the results of X-ray diffraction patterns and X-ray photoelectric spectra, it is concluded that the excellent electrical performance is related to the formation of an oxygen-deficient LiNbO_3-x layer on the sidewall surface during the wet chemical etching process, which is a conductive layer that reduces the thickness of the "dead" layer between the side electrodes and the LiNbO₃ cell and rectifies the diode-like wall currents with an onset voltage reduced from 1.23 to 0.28 V. These results prove the high-density integration of ferroelectric domain-wall memories at the nanoscale and provide a new strategy applicable to the development of LiNbO₃ photonic devices.