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The first report on ion transport through atomic sieves of atomically-thin 2D material is provided to solve critical limitations of electrochemical random-access memory (ECRAM) devices.

Morphotropic phase boundaries (MPBs) show substantial piezoelectric and dielectric responses, which have practical applications. The predicted existence of MPB in HfO2-ZrO2 solid solution thin film has provided a new way to increase the dielectric properties of a silicon-compatible device. Here, we present a new fabrication design by which the density of MPB and consequently the dielectric constant of HfO2-ZrO2 thin film was considerably increased. The density of MPB was controlled by fabrication of a 10-nm [1 nm-Hf0.5Zr0.5O2 (Ferroelectric)/1 nm-ZrO2 (Antiferroelectric)] nanolaminate followed by an appropriate annealing process. The coexistence of orthorhombic and tetragonal structures, which are the origins of ferroelectric (FE) and antiferroelectric (AFE) behaviors, respectively, was structurally confirmed, and a double hysteresis loop that originates from AFE ordering, with some remnant polarization that originates from FE ordering, was observed in P-E curve. A remarkable increase in dielectric constant compared to the conventional HfO2-ZrO2 thin film was achieved by controlling the FE-AFE ratio. The fabrication process was performed at low temperature and the device is compatible with silicon technology, so the new design yields a device that has possible applications in near-future electronics.

Recently, based on the phase-field modeling, it was predicted that Hf1-xZrxO2 (HZO) exhibits the morphotropic phase boundary (MPB) in its compositional phase diagram. Here, we investigate the effect of structural changes between tetragonal (t) and orthorhombic (o) phases on the ferroelectric and dielectric properties of HZO films to probe the existence of MPB region. The structural analysis show that by adjusting the ozone dosage during the atomic layer deposition process and annealing conditions, different ratios of t- to o-phases (f_(t/o) ) were achieved which consequently affect the ferroelectric and dielectric properties of the samples. Polarization versus electric field measurements show a remarkable increase in ferroelectric characteristics (Pr and Ec) of the sample that contains the minimum t-phase fraction (f_(t/o)~ 0.04). This sample shows the lowest dielectric constant compared to the other samples which is due to the formation of ferroelectric o-phase. The sample that contains the maximum f_(t/o)~ 0.41 demonstrates the highest dielectric response. By adjusting the f_(t/o), a large dielectric constant of ~ 55 is achieved. Our study reveals a direct relation between f_(t/o) and dielectric constant of HZO thin films which can be understood by considering the density of MPB region.

A wake-up free Hf0.5Zr0.5O2 (HZO) ferroelectric film with the highest remnant polarization (Pr) value to-date was achieved through tuning of the ozone pulse duration, the annealing process, and the metal/insulator interface. The ozone dosage during the atomic layer deposition of HZO films appears to be a crucial parameter in suppressing the mechanisms driving the wake-up effect. A tungsten capping electrode with a relatively low thermal expansion coefficient enables the induction of an in-plane tensile strain, which increases the formation of the orthorhombic phase while decreasing the formation of the monoclinic phase during the cooling step of the annealing process. Therefore, increasing the annealing temperature TA followed by rapid cooling to room temperature resulted in a substantial increase in the 2Pr value (64 uC/cm2). However, the leakage current increased considerably, which can affect the performance of metal-insulator-metal (MIM) devices. To reduce the leakage current while maintaining the mechanical stress during thermal annealing, a 10 nm Pt layer was inserted between the W/HZO bottom interface. This resulted in a ~ 20-fold decrease in the leakage current while the 2Pr value remained almost constant (~ 60 uC/cm2). The increase in barrier height at the Pt/HZO interface compared to that of the W/HZO interface coupled with the suppression of the formation of interfacial oxides (WOx) by the introduction of a Pt/HZO interface serves to decrease the leakage current.

Wake-up effect is still an obstacle in the commercialization of hafnia-based ferroelectric thin films. In this work, we investigate the effect of defects, controlled by ozone dosage, on the field cycling behavior of the atomic layer deposited Hf0.5Zr0.5O2 (HZO) films. A nearly wake-up free device was achieved after reduction of carbon contamination and oxygen defects by increasing the ozone dosage. The sample which was grown at 30 sec ozone pulse duration shows about 98% of the woken-up Pr at the pristine state while those grown below 5 sec ozone pulse time show a pinched hysteresis loop, undergone a large wake-up effect. This behavior is attributed to the increase in oxygen vacancy and carbon concentration in the films deposited at insufficient O3 dosage which was confirmed by x-ray photoelectron spectroscopy (XPS). X-ray diffraction (XRD) scan shows that the increase of ozone pulse time yields in the reduction of tetragonal phase; therefore, the dielectric constant reduces. The I-V measurements reveal the increase of current density as the ozone dosage decreases which might be due to the generation of oxygen vacancies in the deposited film. Finally, we have investigated the dynamics of wake-up effect and it appears to be explained well by Johnson-Mehl-Avrami-Kolmogoroff model which is based on structural phase transformation.