Stabilizing the ferroelectric phase in HfO2-based films sputtered from ceramic targets under ambient oxygen.

Thin film metal-insulator-metal capacitors with undoped hafnium oxide and a mixture of hafnium and zirconium oxides are prepared by sputtering from ceramic targets. The influence of the oxygen concentration while sputtering and of the zirconium concentration on the ferroelectric properties is characterized by electrical and structural methods. Depending on the ambient oxygen, the thin undoped hafnium oxide films show distinct ferroelectric properties. The interplay of oxygen and zirconia could improve the ferroelectric properties. By varying the ambient oxygen and zirconia concentration in the films, stabilization of the tetragonal, orthorhombic or monoclinic phase is possible. This phase stabilization is strongly influenced by the pre-existing phase and size of the nanocrystallites in the as-deposited films. In conclusion, the impact of the film stress coming from oxygen vacancies and oxygen interstitials is correlated with the phase and ferroelectric properties.

Fluid Imprint and Inertial Switching in Ferroelectric La:HfO2 Capacitors.

Ferroelectric (FE) HfO2-based thin films, which are considered as one of the most promising material systems for memory device applications, exhibit an adverse tendency for strong imprint. Manifestation of imprint is a shift of the polarization-voltage (P-V) loops along the voltage axis due to the development of an internal electric bias, which can lead to the failure of the writing and retention functions. Here, to gain insight into the mechanism of the imprint effect in La-doped HfO2 (La:HfO2) capacitors, we combine the pulse switching technique with high-resolution domain imaging by means of piezoresponse force microscopy. This approach allows us to establish a correlation between the macroscopic switching characteristics and domain time-voltage-dependent behavior. It has been shown that the La:HfO2 capacitors exhibit a much more pronounced imprint compared to Pb(Zr,Ti)O3-based FE capacitors. Also, in addition to conventional imprint, which evolves with time in the poled capacitors, an easily changeable imprint, termed as "fluid imprint", with a strong dependence on the switching prehistory and measurement conditions, has been observed. Visualization of the domain structure reveals a specific signature of fluid imprint-continuous switching of polarization in the same direction as the previously applied field that continues a long time after the field was turned off. This effect, termed as "inertial switching", is attributed to charge injection and subsequent trapping at defect sites at the film-electrode interface.

Unveiling the double-well energy landscape in a ferroelectric layer.

The properties of ferroelectric materials, which were discovered almost a century ago1, have led to a huge range of applications, such as digital information storage2, pyroelectric energy conversion3 and neuromorphic computing4,5. Recently, it was shown that ferroelectrics can have negative capacitance6-11, which could improve the energy efficiency of conventional electronics beyond fundamental limits12-14. In Landau-Ginzburg-Devonshire theory15-17, this negative capacitance is directly related to the double-well shape of the ferroelectric polarization-energy landscape, which was thought for more than 70 years to be inaccessible to experiments18. Here we report electrical measurements of the intrinsic double-well energy landscape in a thin layer of ferroelectric Hf0.5Zr0.5O2. To achieve this, we integrated the ferroelectric into a heterostructure capacitor with a second dielectric layer to prevent immediate screening of polarization charges during switching. These results show that negative capacitance has its origin in the energy barrier in a double-well landscape. Furthermore, we demonstrate that ferroelectric negative capacitance can be fast and hysteresis-free, which is important for prospective applications19. In addition, the Hf0.5Zr0.5O2 used in this work is currently the most industry-relevant ferroelectric material, because both HfO2 and ZrO2 thin films are already used in everyday electronics20. This could lead to fast adoption of negative capacitance effects in future products with markedly improved energy efficiency.

Genuinely Ferroelectric Sub-1-Volt-Switchable Nanodomains in Hf xZr(1- x)O2 Ultrathin Capacitors.

The new class of fully silicon-compatible hafnia-based ferroelectrics with high switchable polarization and good endurance and thickness scalability shows a strong promise for new generations of logic and memory devices. Among other factors, their competitiveness depends on the power efficiency that requires reliable low-voltage operation. Here, we show genuine ferroelectric switching in Hf xZr(1- x)O2 (HZO) layers in the application-relevant capacitor geometry, for driving signals as low as 800 mV and coercive voltage below 500 mV. Enhanced piezoresponse force microscopy with sub-picometer sensitivity allowed for probing individual polarization domains under the top electrode and performing a detailed analysis of hysteretic switching. The authentic local piezoelectric loops and domain wall movement under bias attest to the true ferroelectric nature of the detected nanodomains. The systematic analysis of local piezoresponse loop arrays reveals a totally unexpected thickness dependence of the coercive fields in HZO capacitors. The thickness decrease from 10 to 7 nm is associated with a remarkably strong decrease of the coercive field, with about 50% of the capacitor area switched at coercive voltages ≤0.5 V. Our explanation consistent with the experimental data involves a change of mechanism of nuclei-assisted switching when the thickness decreases below 10 nm. The practical implication of this effect is a robust ferroelectric switching under the millivolt-range driving signal, which is not expected for the standard coercive voltage scaling law. These results demonstrate a strong potential for further aggressive thickness reduction of HZO layers for low-power electronics.