Electrically induced cancellation and inversion of piezoelectricity in ferroelectric Hf0.5Zr0.5O2.

HfO2-based thin films hold huge promise for integrated devices as they show full compatibility with semiconductor technologies and robust ferroelectric properties at nanometer scale. While their polarization switching behavior has been widely investigated, their electromechanical response received much less attention so far. Here, we demonstrate that piezoelectricity in Hf0.5Zr0.5O2 ferroelectric capacitors is not an invariable property but, in fact, can be intrinsically changed by electrical field cycling. Hf0.5Zr0.5O2 capacitors subjected to ac cycling undergo a continuous transition from a positive effective piezoelectric coefficient d33 in the pristine state to a fully inverted negative d33 state, while, in parallel, the polarization monotonically increases. Not only can the sign of d33 be uniformly inverted in the whole capacitor volume, but also, with proper ac training, the net effective piezoresponse can be nullified while the polarization is kept fully switchable. Moreover, the local piezoresponse force microscopy signal also gradually goes through the zero value upon ac cycling. Density functional theory calculations suggest that the observed behavior is a result of a structural transformation from a weakly-developed polar orthorhombic phase towards a well-developed polar orthorhombic phase. The calculations also suggest the possible occurrence of a non-piezoelectric ferroelectric Hf0.5Zr0.5O2. Our experimental findings create an unprecedented potential for tuning the electromechanical functionality of ferroelectric HfO2-based devices.

Cycling Waveform Dependent Wake-Up and ON/OFF Ratio in Al2O3/Hf0.5Zr0.5O2 Ferroelectric Tunnel Junction Devices.

The wake-up behavior and ON/OFF current ratio of TiN-Al2O3-Hf0.5Zr0.5O2-W ferroelectric tunnel junction (FTJ) devices were investigated for different wake-up voltage waveforms. We studied triangular and square waves, as well as square pulse trains of equal or unequal voltage amplitudes for positive and negative polarities. We find that the wake-up behavior in these FTJ stacks is highly influenced by the field cycling waveform. A square waveform is observed to provide wake-up with the lowest number of cycles, concomitantly resulting in higher remnant polarization and a higher ON/OFF ratio in the devices, compared to a triangular waveform. We further show that wake-up is dependent on the number of cycles rather than the total time of the applied electric field during cycling. We also demonstrate that different voltage magnitudes are necessary for positive and negative polarities during field cycling for efficient wake-up. Utilizing an optimized waveform with unequal magnitudes for the two polarities during field cycling, we achieve a reduction in wake-up cycles and a large enhancement of the ON/OFF ratio from ∼5 to ∼35 in our ferroelectric tunnel junctions.

In-Situ Temperature Measurement on CMOS Integrated Micro-Hotplates for Gas Sensing Devices.

Metal oxide gas sensors generally need to be operated at elevated temperatures, up to and above 400 °C. Following the need for miniaturization of gas sensors and implementation into smart devices such as smartphones or wireless sensor nodes, recently complementary metal-oxide-semiconductor (CMOS) process-based micro electromechanical system (MEMS) platforms (micro-hotplates, µhps) have been developed to provide Joule heating of metal oxide sensing structures on the microscale. Heating precision and possible spatial temperature distributions over the µhp are key issues potentially affecting the performance of the overall gas sensor device. In this work, we use Raman spectroscopy to directly (in-situ and in-operando) measure the temperature of CMOS-based µhps during the application of electric current for Joule heating. By monitoring the position of the Raman mode of silicon and applying the theoretical framework of anharmonic phonon softening, we demonstrate that state-of-the-art µhps are able to reach the set temperature with an error below 10%, albeit with significant spatial temperature variations on the hotplate. This work demonstrates the potential of Raman spectroscopy for in-situ and in-operando temperature measurements on Si-based devices, an aspect of high relevance for micro- and nano-electronic device producers, opening new possibilities in process and device control.

Storage of Renewable Energy by Reduction of CO2 with Hydrogen.

The main difference between the past energy economy during the industrialization period which was mainly based on mining of fossil fuels, e.g. coal, oil and methane and the future energy economy based on renewable energy is the requirement for storage of the energy fluxes. Renewable energy, except biomass, appears in time- and location-dependent energy fluxes as heat or electricity upon conversion. Storage and transport of energy requires a high energy density and has to be realized in a closed materials cycle. The hydrogen cycle, i.e. production of hydrogen from water by renewable energy, storage and use of hydrogen in fuel cells, combustion engines or turbines, is a closed cycle. However, the hydrogen density in a storage system is limited to 20 mass% and 150 kg/m(3) which limits the energy density to about half of the energy density in fossil fuels. Introducing CO(2) into the cycle and storing hydrogen by the reduction of CO(2) to hydrocarbons allows renewable energy to be converted into synthetic fuels with the same energy density as fossil fuels. The resulting cycle is a closed cycle (CO(2) neutral) if CO(2) is extracted from the atmosphere. Today's technology allows CO(2) to be reduced either by the Sabatier reaction to methane, by the reversed water gas shift reaction to CO and further reduction of CO by the Fischer-Tropsch synthesis (FTS) to hydrocarbons or over methanol to gasoline. The overall process can only be realized on a very large scale, because the large number of by-products of FTS requires the use of a refinery. Therefore, a well-controlled reaction to a specific product is required for the efficient conversion of renewable energy (electricity) into an easy to store liquid hydrocarbon (fuel). In order to realize a closed hydrocarbon cycle the two major challenges are to extract CO(2) from the atmosphere close to the thermodynamic limit and to reduce CO(2) with hydrogen in a controlled reaction to a specific hydrocarbon. Nanomaterials with nanopores and the unique surface structures of metallic clusters offer new opportunities for the production of synthetic fuels.