Ferroelectricity Induced by Oxygen Vacancies in Rhombohedral ZrO_(2) Thin Films

Rhombohedral phase Hf_(x)Zr_(1.x)O_(2)(HZO,x from 0 to 1)films are promising for achieving robust ferroelectric polarization without the need for an initial wake-up pre-cycling,as is normally the case for the more commonly studied orthorhombic phase.However,a large spontaneous polarization observed in rhombohedral films is not fully understood,and there are also large discrepancies between experimental and theoretical predictions.In this work,in rhombohedral ZrO_(2)thin films,we show that oxygen vacancies are not only a key factor for stabilizing the phase,but they are also a source of ferroelectric polarization in the films.This is shown experimentally through the investigation of the structural properties,chemical composition and the ferroelectric properties of the films before and after an annealing at moderate temperature(400℃)in an oxygen environment to reduce the V_(o)concentration compared.The experimental work is supported by density functional theory(DFT)calculations which show that the rhombohedral phase is the most stable one in highly oxygen defective ZrO_(2)films.The DFT calculations also show that V_(o)contribute to the ferroelectric polarization.Our findings reveal the importance of V_(o)for stabilizing rhombohedral ZrO_(2)thin films with superior ferroelectric properties.