Sub-0.5 nm Equivalent Oxide Thickness Scaling for Si-Doped Zr1–xHfxO2 Thin Film without Using Noble Metal Electrode

The dielectric properties of the Si-doped Zr1–xHfxO2 thin films were investigated over a broad compositional range with the goal of improving their properties for use as DRAM capacitor materials. The Si-doped Zr1–xHfxO2 thin films were deposited on TiN bottom electrodes by atomic layer deposition using a TEMA-Zr/TEMA-Hf mixture precursor for deposition of Zr1–xHfxO2 film and Tris-EMASiH as a Si precursor. The Si stabilizer increased the tetragonality and the dielectric constant; however, at high fractions of Si, the crystal structure degraded to amorphous and the dielectric constant decreased. Doping with Si exhibited a larger influence on the dielectric constant at higher Hf content. A Si-doped Hf-rich Zr1–xHfxO2 thin film, with tetragonal structure, exhibited a dielectric constant of about 50. This is the highest value among all reported results for Zr and Hf oxide systems, and equivalent oxide thickness (EOT) value of under 0.5 nm could be obtained with a leakage current of under 10–7 A·cm–2, which is the lowest EOT value ever reported for a DRAM storage capacitor system without using a noble-metal-based electrode.