Abstract
Lead zirconate titanate Pb(Zr0.50Ti0.50)O3 (PZT) thin films were deposited by a polymeric chemical method on Pt(111)/ Ti/SiO2/Si substrates to understand the mechanisms of phase transformations in these films. PZT films pyrolyzed at temperatures higher than 350℃ present a coexistence of pyrochlore and perovskite phases, while only perovskite phase is present in films pyrolyzed at temperatures lower than 300℃. For films where the pyrochlore and perovskite phase coexists the amount of pyrochlore phase decreases from top surface to the bottom film-electrode interface and the PZT structure near top surface are Ti-rich compositions while near the bottom film-electrode interface the compositions are Zr-rich. For pyrochlore-free PZT thin film, a small (100) orientation tendency near the film-electrode interface was observed.
Highlights
Over the past 50 years, the lead zirconate titanate Pb(Zr,Ti)O3 (PZT) was probably one of the most studied ferroelectric materials due to their excellent physical properties [1]
In contrast to new problems associated to downscaling of the solid-state electronics, some problems related to the synthesis of PZT thin films are periodically revisited providing activities to produce high performance devices
The splitting of (002) and (200) reflections in Figure 1(b) for PZT films pyrolyzed at 400 ̊C and 450 ̊C clearly indicates a shift toward the tetragonal side in the composition-temperature phase diagram of the PZT system [1]. This implies a Ti-rich PZT composition (Zr/Ti < 1) in comparison to the nominal Pb(Zr0.50Ti0.50)O3 composition (Zr/Ti = 1), which would enrich the pyrochlore phase and reduce the perovskite phase in Zr ions. These results strongly indicate that the growth of a Zr-rich pyrochlore phase Pb2(Zr1−xTix)2O6 (Zr/Ti > 1) is more energetically favorable for films pyrolyzed at 400 ̊C and 450 ̊C
Summary
Over the past 50 years, the lead zirconate titanate Pb(Zr,Ti)O3 (PZT) was probably one of the most studied ferroelectric materials due to their excellent physical properties [1]. The crystallization of PZT films using low temperature deposition techniques occurs from the amorphous structure that first transforms into an intermediate non-ferroelectric phase and transform into the perovskite phase after an adequate pyrolysis and thermal annealing. This transformation kinetic depends on the method used to prepare thin films. This undesirable non-ferroelectric phase is often described as pyrochlore, sometimes referred as Pb-deficient fluorite phase [9]. The presence of this phase degrades the most important ferroelectric properties of the film and must be avoided during the crystallization
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