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Title: Analysis of Performance Instabilities of Hafnia‐Based Ferroelectrics Using Modulus Spectroscopy and Thermally Stimulated Depolarization Currents

The discovery of the ferroelectric orthorhombic phase in doped hafnia films has sparked immense research efforts. Presently, a major obstacle for hafnia's use in high‐endurance memory applications like nonvolatile random‐access memories is its unstable ferroelectric response during field cycling. Different mechanisms are proposed to explain this instability including field‐induced phase change, electron trapping, and oxygen vacancy diffusion. However, none of these is able to fully explain the complete behavior and interdependencies of these phenomena. Up to now, no complete root cause for fatigue, wake‐up, and imprint effects is presented. In this study, the first evidence for the presence of singly and doubly positively charged oxygen vacancies in hafnia–zirconia films using thermally stimulated currents and impedance spectroscopy is presented. Moreover, it is shown that interaction of these defects with electrons at the interfaces to the electrodes may cause the observed instability of the ferroelectric performance.

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Author(s) / Creator(s):
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Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Advanced Electronic Materials
Medium: X
Sponsoring Org:
National Science Foundation
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  2. Abstract

    Silicon doped hafnium oxide was the material used in the original report of ferroelectricity in hafnia in 2011. Since then, it has been subject of many further publications including the demonstration of the world's first ferroelectric field‐effect transistor in the state‐of‐the‐art 28 nm technology. Though many studies are conducted with a strong focus on application in memory devices, a comprehensive study on structural stability in these films remains to be seen. In this work, a film thickness of about 36 nm, instead of the 10 nm used in most previous studies, is utilized to carefully probe how the concentration range impacts the evolution of phases, the dopant distribution, the field cycling effects, and their interplay in the macroscopic ferroelectric response of the films. Si:HfO2appears to be a rather fragile system: different phases seem close in energy and the system is thus rich in competing phenomena. Nonetheless, it offers ferroelectricity or field‐induced ferroelectricity for elevated annealing conditions up to 1000 °C. Similar to the measures taken for conventional ferroelectrics such as lead zirconate titanate, engineering efforts to guarantee stable interfaces and stoichiometry are mandatory to achieve stable performance in applications such as ferroelectric memories, supercapacitors, or energy harvesting devices.

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  3. Ferroelectric hafnium oxides are poised to impact a wide range of microelectronic applications owing to their superior thickness scaling of ferroelectric stability and compatibility with mainstream semiconductors and fabrication processes. For broad-scale impact, long-term performance and reliability of devices using hafnia will require knowledge of the phases present and how they vary with time and use. In this Perspective article, the importance of phases present on device performance is discussed, including the extent to which specific classes of devices can tolerate phase impurities. Following, the factors and mechanisms that are known to influence phase stability, including substituents, crystallite size, oxygen point defects, electrode chemistry, biaxial stress, and electrode capping layers, are highlighted. Discussions will focus on the importance of considering both neutral and charged oxygen vacancies as stabilizing agents, the limited biaxial strain imparted to a hafnia layer by adjacent electrodes, and the strong correlation of biaxial stress with resulting polarization response. Areas needing additional research, such as the necessity for a more quantitative means to distinguish the metastable tetragonal and orthorhombic phases, quantification of oxygen vacancies, and calculation of band structures, including defect energy levels for pure hafnia and stabilized with substituents, are emphasized.

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  4. Since 2011, ferroelectric HfO2has attracted growing interest in both fundamental and application oriented groups. In this material, noteworthy wake‐up and fatigue effects alter the shape of the polarization hysteresis loop during field cycling. Such changes are problematic for application of HfO2to ferroelectric memories, which require stable polarization hystereses. Herein, electrical and structural techniques are implemented to unveil how cyclic switching changes nanoscale film structure, which modifies the polarization hysteresis. Impedance spectroscopy and scanning transmission electron microscopy identify regions with different dielectric and conductive properties in films at different cycling stages, enabling development of a structural model to explain the wake‐up and fatigue phenomena. The wake‐up regime arises due to changes in bulk and interfacial structuring: the bulk undergoes a phase transformation from monoclinic to orthorhombic grains, and the interfaces show changes in and diminishment of a nonuniform, defect rich, tetragonal HfO2layer near the electrodes. The evolution of these aspects of structuring contributes to the increase inPrand the opening of the constrictedPVhysteresis that are known to occur with wake‐up. The onset of the fatigue regime is correlated to an increasing concentration of bulk defects, which are proposed to pin domain walls.

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