Structure and composition of the ferroelectric Pb(Zr, Ti)O3 layers in a capacitor of the ferroelectric random-access memory (FeRAM) device having a density of 64 k were investigated by transmission electron microscopy (TEM) together with the energy-dispersive spectroscopy (EDS) technique. The 250 nm thick PZT layer derived by the sol-gel route showed a 2–3% Pb-deficient, 3–4% Ti-deficient, and 5–7% Zr-excess composition at the top electrode interface compared to the bulk composition when they were as-fabricated. The local compositional nonuniformity became more critical as the integration process proceeded, which seriously degraded the ferroelectric hysteresis and the device yield. The major cause of the compositional variation was the outward diffusion of Pb through the capping barrier TiO2 layer during annealing at 650 °C. The AlN capping barrier layer was also not effective in suppressing the diffusion of Pb. However, the Al2O3/TiO2 double capping layer was very effective in suppressing the outward diffusion of Pb, and excellent ferroelectric characteristic was expected.