Enhanced Switching Reliability of Hf0.5Zr0.5O2 Ferroelectric Films Induced by Interface Engineering.

Ferroelectric materials have been widely researched for applications in memory and energy storage. Among these materials and benefiting from their excellent chemical compatibility with complementary metal-oxide-semiconductor (CMOS) devices, hafnia-based ferroelectric thin films hold great promise for highly scaled semiconductor memories, including nonvolatile ferroelectric capacitors and transistors. However, variation in the switched polarization of this material during field cycling and a limited understanding of the responsible mechanisms have impeded their implementation in technology. Here, we show that ferroelectric Hf0.5Zr0.5O2 (HZO) capacitors that are nearly free of polarization "wake-up"─a gradual increase in switched polarization as a function of the number of switching cycles─can be achieved by introducing ultrathin HfO2 buffer layers at the HZO/electrodes interface. High-resolution transmission electron microscopy (HRTEM) reveals crystallite sizes substantially greater than the film thickness for the buffer layer capacitors, indicating that the presence of the buffer layers influences the crystallization of the film (e.g., a lower ratio of nucleation rate to growth rate) during postdeposition annealing. This evidently promotes the formation of a polar orthorhombic (O) phase in the as-fabricated buffer layer samples. Synchrotron X-ray diffraction (XRD) reveals the conversion of the nonpolar tetragonal (T) phase to the polar orthorhombic (O) phase during electric field cycling in the control (no buffer) devices, consistent with the polarization wake-up observed for these capacitors. The extent of T-O transformation in the nonbuffer samples is directly dependent on the duration over which the field is applied. These results provide insight into the role of the HZO/electrodes interface in the performance of hafnia-based ferroelectrics and the mechanisms driving the polarization wake-up effect.

Nanocrystallite Seeding of Metastable Ferroelectric Phase Formation in Atomic Layer-Deposited Hafnia-Zirconia Alloys.

Hafnia-based ferroelectric thin films are promising for semiconductor memory and neuromorphic computing applications. Amorphous, as-deposited, thin-film binary alloys of HfO2 and ZrO2 transform to the metastable, orthorhombic ferroelectric phase during post-deposition annealing and cooling. This transformation is generally thought to involve formation of a tetragonal precursor phase that distorts into the orthorhombic phase during cooling. In this work, we systematically study the effects of atomic layer deposition (ALD) temperature on the ferroelectricity of post-deposition-annealed Hf0.5Zr0.5O2 (HZO) thin films. Seed crystallites having interplanar spacings consistent with the polar orthorhombic phase are observed by a plan-view transmission electron microscope in HZO thin films deposited at an elevated ALD temperature. After ALD under conditions that promote formation of these nanocrystallites, high-polarization (Pr > 18 µC/cm2) ferroelectric switching is observed after rapid thermal annealing (RTA) at low temperature (350 °C). These results indicate the presence of minimal non-ferroelectric phases retained in the films after RTA when the ALD process forms nanocrystalline particles that seed subsequent formation of the polar orthorhombic phase.

Strain Dependent Electronic Structure and Band Offset Tuning at Heterointerfaces of ASnO3 (A=Ca, Sr, and Ba) and SrTiO3.

The valence band (VB) electronic structure and VB alignments at heterointerfaces of strained epitaxial stannate ASnO3 (A=Ca, Sr, and Ba) thin films are characterized using in situ X-ray and ultraviolet photoelectron spectroscopies, with band gaps evaluated using spectroscopic ellipsometry. Scanning transmission electron microscopy with geometric phase analysis is used to resolve strain at atomic resolution. The VB electronic structure is strain state dependent in a manner that correlated with a directional change in Sn-O bond lengths with strain. However, VB offsets are found not to vary significantly with strain, which resulted in ascribing most of the difference in band alignment, due to a change in the band gaps with strain, to the conduction band edge. Our results reveal significant strain tuning of conduction band offsets using epitaxial buffer layers, with strain-induced offset differences as large as 0.6 eV possible for SrSnO3. Such large conduction band offset tunability through elastic strain control may provide a pathway to minimize the loss of charge confinement in 2-dimensional electron gases and enhance the performance of photoelectrochemical stannate-based devices.