Unravelling and controlling hidden imprint fields in ferroelectric capacitors

Ferroelectric materials have a spontaneous polarization that can point along energetically equivalent, opposite directions. However, when ferroelectric layers are sandwiched between different metallic electrodes, asymmetric electrostatic boundary conditions may induce the appearance of an electric field (imprint field, Eimp) that breaks the degeneracy of the polarization directions, favouring one of them. This has dramatic consequences on functionality of ferroelectric-based devices such as ferroelectric memories or photodetectors. Therefore, to cancel out the Eimp, ferroelectric components are commonly built using symmetric contact configuration. Indeed, in this symmetric contact configuration, when measurements are done under time-varying electric fields of relatively low frequency, an archetypical symmetric single-step switching process is observed, indicating Eimp ≈ 0. However, we report here on the discovery that when measurements are performed at high frequency, a well-defined double-step switching is observed, indicating the presence of Eimp. We argue that this frequency dependence originates from short-living head-to-head or tail-to-tail ferroelectric capacitors in the device. We demonstrate that we can modulate Eimp and the life-time of head-to-head or tail-to-tail polarization configurations by adjusting the polarization screening charges by suitable illumination. These findings are of relevance to understand the effects of internal electric fields on pivotal ferroelectric properties, such as memory retention and photoresponse.