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 µC/cm 2 ). 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 µC/cm 2 ). 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. Herein, the effect of defects, controlled by ozone dosage, on the field cycling behavior of the atomic layer deposited Hf0.5Zr0.5O2 (HZO) films is investigated. A nearly wake‐up free device is achieved after reduction of carbon contamination and oxygen defects by increasing the ozone dosage. The sample which is grown at 30 s ozone pulse duration shows about 97% of the woken‐up Pr at the pristine state whereas that grown below 5 s ozone pulse time shows a pinched hysteresis loop, that underwent 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 is confirmed by X‐ray photoelectron spectroscopy (XPS). The X‐ray diffraction (XRD) scan shows that the increase in ozone pulse time yields the reduction of tetragonal phase; therefore, the dielectric constant reduces. The I–V measurements reveal the increase in current density as the ozone dosage decreases, which might be due to the generation of oxygen vacancies in the deposited film. Finally, the dynamics of wake‐up effect is investigated, and it appears to be explained well by the Johnson–Mehl–Avrami–Kolmogoroff model, which is based on structural phase transformation.
Hafnium oxide (HfO2) is one of the mature high‐k dielectrics that has been standing strong in the memory arena over the last two decades. Its dielectric properties have been researched rigorously for the development of flash memory devices. In this review, the application of HfO2 in two main emerging nonvolatile memory technologies is surveyed, namely resistive random access memory and ferroelectric memory. How the properties of HfO2 equip the former to achieve superlative performance with high‐speed reliable switching, excellent endurance, and retention is discussed. The parameters to control HfO2 domains are further discussed, which can unleash the ferroelectric properties in memory applications. Finally, the prospect of HfO2 materials in emerging applications, such as high‐density memory and neuromorphic devices are examined, and the various challenges of HfO2‐based resistive random access memory and ferroelectric memory devices are addressed with a future outlook.
In this study, we investigate the effects of various electrodes on the ferroelectric properties of ultrathin HfZrOx (HZO) films. The ferroelectric polarization is totally suppressed in the HZO films with TiN and W bottom electrodes when the film thickness is below 5 nm. These results can be attributed to the formation of a dead layer at the bottom electrode/HZO interface during the atomic layer deposition (ALD) and annealing processes. On the other hand, the HZO film with a Pt bottom electrode shows an excellent P–E loop with a very high switchable polarization (2Pr) of 42.5 μC/cm2 even at a film thickness of 2.5 nm. Through the short pulse switching technique, we confirm the formation of a thick dead layer in the HZO films with TiN and W electrodes, which inhibits the formation of the orthorhombic phase in these ultrathin HZO films. This implies that the ferroelectric property of ultrathin HZO films can be improved by choosing an appropriate electrode material capable of suppress ing the formation of a dead layer.
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