ABSTRACT
Crystalline materials with broken inversion symmetry can exhibit a spontaneous electric polarization, which originates from a microscopic electric dipole moment. Long-range polar or anti-polar order of such permanent dipoles gives rise to ferroelectricity or antiferroelectricity, respectively. However, the recently discovered antiferroelectrics of fluorite structure (HfO2 and ZrO2) are different: A non-polar phase transforms into a polar phase by spontaneous inversion symmetry breaking upon the application of an electric field. Here, we show that this structural transition in antiferroelectric ZrO2 gives rise to a negative capacitance, which is promising for overcoming the fundamental limits of energy efficiency in electronics. Our findings provide insight into the thermodynamically forbidden region of the antiferroelectric transition in ZrO2 and extend the concept of negative capacitance beyond ferroelectricity. This shows that negative capacitance is a more general phenomenon than previously thought and can be expected in a much broader range of materials exhibiting structural phase transitions.
ABSTRACT
The Landau theory of phase transitions predicts the presence of a negative capacitance in ferroelectric materials based on a mean-field approach. While recent experimental results confirm this prediction, the microscopic origin of negative capacitance in ferroelectrics is often debated. This study provides a simple, physical explanation of the negative capacitance phenomenon-i.e., 'S'-shaped polarization vs. electric field curve-without having to invoke the Landau phenomenology. The discussion is inspired by pedagogical models of ferroelectricity as often presented in classic text-books such as the Feynman lectures on Physics and the Introduction of Solid State Physics by Charles Kittel, which are routinely used to describe the quintessential ferroelectric phenomena such as the Curie-Weiss law and the emergence of spontaneous polarization below the Curie temperature. The model presented herein is overly simplified and ignores many of the complex interactions in real ferroelectrics; however, this model reveals an important insight: The polarization catastrophe phenomenon that is required to describe the onset of ferroelectricity naturally leads to the thermodynamic instability that is negative capacitance. Considering the interaction of electric dipoles and saturation of the dipole moments at large local electric fields we derive the full 'S'-curve relating the ferroelectric polarization and the electric field, in qualitative agreement with Landau theory.
