Novel HfO2-Based Multilayer Stack for Devices with Enhanced Capacitance

Abstract

Recent discovery of ferroelectricity from non-centrosymmetric orthorhombic phase (Pca21) of Hf/Zr oxides [1] has brought enormous research interests and activities because the material compatibility with CMOS process and its scalability to a few nm thickness, which have been critical issues for introducing perovskites ferroelectric (FE) materials in nanoscale devices. Physical concept of “negative capacitance” in FE materials when stacked with dielectrics (DE) has been proposed to enhance the total capacitance larger than that of DE only [2,3] and has been demonstrated in DE-FE stacks such as Al2O3/Hf0.5Zr0.5O2 or Ta2O5/Hf0.5Zr0.5O2 via transient measurement [4,5]. However, stacks with amorphous Al2O3 DE layer having relatively low dielectric constant were vulnerable to irreversible charge injection from electrodes into the DE-FE interface and thus hysteresis-free operation of the capacitor was only limited to short pulse condition below 1μs. Also Ta2O5 DE layer is often found to be defective and the film easily becomes leaky with repeated cycles.Here we propose novel DE-FE stack based on all crystallized Hf/Zr oxides where polymorphic Hf/Zr oxides have three dominant phases, monoclinic (P21/c), orthorhombic (Pca21), and tetragonal (P42/nmc) and by varying parameters such as Zr composition and thickness in initial amorphous film, the oxides can be crystallized in phase-selective way. We employ the tetragonal phase of Hf/Zr oxide for DE layer which possesses high-k value above 30 and wide bandgap about 5.4 eV ensuring low leakage current and further enabling thickness scaling. All crystallized DE-FE stacks were fabricated on bottom electrodes via atomic layer deposition of Hf/Zr oxides with compositional variation and subsequent metal deposition and post-metallization-annealing. Electrical data from capacitance vs. voltage and polarization vs. voltage measurements manifests an intermediate characteristic between ferroelectric and anti-ferroelectric ones due to multi-phase layers. Pulsed voltage measurements and structural analyses with XRD and selective area electron diffraction will be presented to assess the proposed stack for devices with enhanced capacitance.