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  1. Free, publicly-accessible full text available February 1, 2025
  2. Abstract Because of its compatibility with semiconductor-based technologies, hafnia (HfO 2 ) is today’s most promising ferroelectric material for applications in electronics. Yet, knowledge on the ferroic and electromechanical response properties of this all-important compound is still lacking. Interestingly, HfO 2 has recently been predicted to display a negative longitudinal piezoelectric effect, which sets it apart from classic ferroelectrics (e.g., perovskite oxides like PbTiO 3 ) and is reminiscent of the behavior of some organic compounds. The present work corroborates this behavior, by first-principles calculations and an experimental investigation of HfO 2 thin films using piezoresponse force microscopy. Further, the simulations show how the chemical coordination of the active oxygen atoms is responsible for the negative longitudinal piezoelectric effect. Building on these insights, it is predicted that, by controlling the environment of such active oxygens (e.g., by means of an epitaxial strain), it is possible to change the sign of the piezoelectric response of the material. 
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  3. Optical techniques for recording and manipulating cellular electrophysiology have advanced rapidly in just a few decades. These developments allow for the analysis of cardiac cellular dynamics at multiple scales while largely overcoming the drawbacks associated with the use of electrodes. The recent advent of optogenetics opens up new possibilities for regional and tissue-level electrophysiological control and hold promise for future novel clinical applications. This article, which emerged from the international NOTICE workshop in 2018 1 , reviews the state-of-the-art optical techniques used for cardiac electrophysiological research and the underlying biophysics. The design and performance of optical reporters and optogenetic actuators are reviewed along with limitations of current probes. The physics of light interaction with cardiac tissue is detailed and associated challenges with the use of optical sensors and actuators are presented. Case studies include the use of fluorescence recovery after photobleaching and super-resolution microscopy to explore the micro-structure of cardiac cells and a review of two photon and light sheet technologies applied to cardiac tissue. The emergence of cardiac optogenetics is reviewed and the current work exploring the potential clinical use of optogenetics is also described. Approaches which combine optogenetic manipulation and optical voltage measurement are discussed, in terms of platforms that allow real-time manipulation of whole heart electrophysiology in open and closed-loop systems to study optimal ways to terminate spiral arrhythmias. The design and operation of optics-based approaches that allow high-throughput cardiac electrophysiological assays is presented. Finally, emerging techniques of photo-acoustic imaging and stress sensors are described along with strategies for future development and establishment of these techniques in mainstream electrophysiological research. 
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  4. Abstract

    Piezoresponse force microscopy (PFM) is widely used for characterization and exploration of the nanoscale properties of ferroelectrics. However, quantification of the PFM signal is challenging due to the convolution of various extrinsic and intrinsic contributions. Although quantification of the PFM amplitude signal has received considerable attention, quantification of the PFM phase signal has not been addressed. A properly calibrated PFM phase signal can provide valuable information on the sign of the local piezoelectric coefficient—an important and nontrivial issue for emerging ferroelectrics. In this work, two complementary methodologies to calibrate the PFM phase signal are discussed. The first approach is based on using a standard reference sample with well‐known independently measured piezoelectric coefficients, while the second approach exploits the electrostatic sample–cantilever interactions to determine the parasitic phase offset. Application of these methodologies to studies of the piezoelectric behavior in ferroelectric HfO2‐based thin‐film capacitors reveals intriguing variations in the sign of the longitudinal piezoelectric coefficient,d33,eff. It is shown that the piezoelectric properties of the HfO2‐based capacitors are inherently sensitive to their thickness, electrodes, as well as deposition methods, and can exhibit wide variations including ad33,effsign change within a single device.

     
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  5. Abstract

    The ferroelectricity in fluorite oxides has gained increasing interest due to its promising properties for multiple applications in semiconductor as well as energy devices. The structural origin of the unexpected ferroelectricity is now believed to be the formation of a non‐centrosymmetric orthorhombic phase with the space group ofPca21. However, the factors driving the formation of the ferroelectric phase are still under debate. In this study, to understand the effect of annealing temperature, the crystallization process of doped HfO2thin films is analyzed using in situ, high‐temperature X‐ray diffraction. The change in phase fractions in a multiphase system accompanied with the unit cell volume increase during annealing could be directly observed from X‐ray diffraction analyses, and the observations give an information toward understanding the effect of annealing temperature on the structure and electrical properties. A strong coupling between the structure and the electrical properties is reconfirmed from this result.

     
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  6. 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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