Characterization of Bi and Fe co-doped PZT capacitors for FeRAM

Ferroelectric random access memory (FeRAM) has been in mass production for over 15 years. Higher polarization ferroelectric materials are needed for future devices which can operate above about 100 °C. With this goal in mind, co-doping of thin Pb(Zr₄₀,Ti₆₀)O₃ (PZT) films with 1 at.% Bi and 1 at.% Fe was examined in order to enhance the ferroelectric properties as well as characterize the doped material. The XRD patterns of PZT-5% BiFeO₃ (BF) and PZT 140-nm thick films showed (111) orientation on (111) platinized Si wafers and a 30 °C increase in the tetragonal to cubic phase transition temperature, often called the Curie temperature, from 350 to 380 °C with co-doping, indicating that Bi and Fe are substituting into the PZT lattice. Raman spectra revealed decreased band intensity with Bi and Fe co-doping of PZT compared to PZT. Polarization hysteresis loops show similar values of remanent polarization, but square-shaped voltage pulse-measured net polarization values of PZT-BF were higher and showed higher endurance to repeated cycling up to 10¹⁰ cycles. It is proposed that Bi and Fe are both in the +3 oxidation state and substituting into the perovskite A and B sites, respectively. Substitution of Bi and Fe into the PZT lattice likely creates defect dipoles, which increase the net polarization when measured by the short voltage pulse positive-up-negative-down (PUND) method.