After the discovery of ferroelectricity in HfO2, many dopants have been incorporated into the material to improve the ferroelectric properties. The binary mixture of HfO2 and ZrO2, HfxZrx−1O2, showed the widest process window in terms of polarization, but other memory related aspects still need improvement. Recently, the co‐doping of La into a mixed Hf0.5Zr0.5O2, La:HZO, was reported to improve the endurance properties further but the explanation spanning both structural and electrical characteristics of La:HZO and their interaction is still missing. In this work, an extensive study of La:HZO with La content ranging from 0 to 4.3 mol% is conducted and resultant stabilization of nonpolar tetragonal phase, coercive field reduction, endurance improvement, stronger retention loss, and less imprinted hysteresis loop is reported with increasing La concentration. The model simultaneously explaining the electrical and structural properties is presented. In ferroelectric capacitor structures, the depolarization fields originating from nonferroelectric layers at the metal/ferroelectric interface are discussed extensively in previous studies but, here, for the first time, the impact of depolarization fields from nonferroelectric regions in the bulk of the ferroelectric material is reported, which is an important element to explain all the observed trends.
We present a hard and soft x-ray photoelectron spectroscopy study of the interface chemistry in pristine TiN/La-doped Hf0.5Zr0.5O2/TiN capacitors. An oxynitride phase (∼1.3 nm) is formed at the top interface, while a TiO2−δ phase was detected near the bottom interface. The oxygen vacancy (VO) concentration is higher at the top interface than in the film due to oxygen scavenging by the top electrode. The VO concentration was also found to increase from ∼1.5 to 1.9 × 1020 cm−3 when increasing La doping from 1.7 to 2.7 mol. %. Two La dopants are compensated by the formation of one positively charged VO.
Lanthanum-doped HfZrO is considered as the ferroelectric material for capacitor structures used in one-transistor-one capacitor nonvolatile memory cells for the development of new generation nonvolatile random-access memory. Here, different capacitor structures are characterized by x-ray photoelectron spectroscopy electrically to determine the electron and hole contribution to the conductivity in these capacitor structures. Experiments related to the minority carrier's injection and charge transport from an n-Si and a p-Si substrate into a lanthanum-doped HfZrO layer show that the conductivity is bipolar. Electrons are injected into La:HfZrO from a negatively biased contact, and accordingly, holes are injected from a positive voltage biased electrode.
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