Dimensional Scaling of Ferroelectric Properties of Hafnia-Zirconia Thin Films: Electrode Interface Effects.

Hafnia-based ferroelectric (FE) thin films are promising candidates for semiconductor memories. However, a fundamental challenge that persists is the lack of understanding regarding dimensional scaling, including thickness scaling and area scaling, of the functional properties and their heterogeneity in these films. In this work, excellent ferroelectricity and switching endurance are demonstrated in 4 nm-thick Hf0.5Zr0.5O2 (HZO) capacitors with molybdenum electrodes in capacitors as small as 65 nm × 45 nm in size. The HZO layer in these capacitors can be crystallized into the ferroelectric orthorhombic phase at the low temperature of 400 °C, making them compatible for back-end-of-line (BEOL) FE memories. With the benefits of thickness scaling, low operation voltage (1.2 V) is achieved with high endurance (>1010 cycles); however, a significant fatigue regime is noted. We observed that the bottom electrode, rather than the top electrode, plays a dominant role in the thickness scaling of HZO ferroelectric behavior. Furthermore, ultrahigh switched polarization (remanent polarization 2Pr ∼ 108 µC cm-2) is observed in some nanoscale devices. This study advances the understanding of dimensional scaling effects in HZO capacitors for high-performance FE memories.

Atomic Layer Deposition of WO3-Doped In2O3 for Reliable and Scalable BEOL-Compatible Transistors.

Tungsten oxide (WO3) doped indium oxide (IWO) field-effect transistors (FET), synthesized using atomic layer deposition (ALD) for three-dimensional integration and back-end-of-line (BEOL) compatibility, are demonstrated. Low-concentration (1∼4 W atom %) WO3-doping in In2O3 films is achieved by adjusting cycle ratios of the indium and tungsten precursors with the oxidant coreactant. Such doping suppresses oxygen deficiency from In2O2.5 to In2O3 stoichiometry with only 1 atom % W, allowing devices to turn off stably and enhancing threshold voltage stability. The ALD IWO FETs exhibit superior performance, including a low subthreshold slope of 67 mV/decade and negligible hysteresis. Strong tunability of the threshold voltage (Vth) is achieved through W concentration tuning, with 2 atom % IWO FETs showing an optimized Vth for enhancement-mode and a high drain current. ALD IWO FETs have remarkable stability under bias stress and nearly ideal performance extending to sub-100 nm channel lengths, making them promising candidates for high-performance monolithic 3D integrated devices.

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.