Lead zirconate titanate (PZT) films with high Nb concentrations (6–13 mol%) were grown by chemical solution deposition. In concentrations up to 8 mol% Nb, the films self-compensate the stoichiometry; single phase films were grown from precursor solutions with 10 mol% PbO excess. Higher Nb concentrations induced multi-phase films unless the amount of excess PbO in the precursor solution was reduced. Phase pure perovskite films were grown with 13 mol% excess Nb with the addition of 6 mol% PbO. Charge compensation was achieved by creating lead vacancies when decreasing excess PbO level; using Kroger-Vink notation, NbTi• are ionically compensated by VPb″ to maintain charge neutrality in heavily Nb-doped PZT films. With Nb doping, films showed suppressed {100} orientation, the Curie temperature decreased, and the maximum in the relative permittivity at the phase transition broadened. The dielectric and piezoelectric properties were dramatically degraded due to increased quantity of the non-polar pyrochlore phase in multi-phase films; εr reduced from 1360 ± 8 to 940 ± 6, and the remanent d33,f value decreased from 112 to 42 pm/V when increasing the Nb concentration from 6 to 13 mol%. Property deterioration was corrected by decreasing the PbO level to 6 mol%; phase pure perovskite films were attained. εr and the remanent d33,f increased to 1330 ± 9 and 106 ± 4 pm/V, respectively. There was no discernable difference in the level of self-imprint in phase pure PZT films with Nb doping. However, the magnitude of the internal field after thermal poling at 150 °C increased significantly; the level of imprint was 30 kV/cm and 11.5 kV/cm in phase pure 6 mol% and 13 mol% Nb-doped films, respectively. The absence of mobile VO••, coupled with the immobile VPb″ in 13 mol% Nb-doped PZT films, leads to lower internal field formation upon thermal poling. For 6 mol% Nb-doped PZT films, the internal field formation was primarily governed by (1) the alignment of (VPb″−VO•• )x and (2) the injection and subsequent electron trapping by Ti4+. For 13 mol% Nb-doped PZT films, hole migration between VPb″ controlled internal field formation upon thermal poling.
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Influence of doping and thickness on domain avalanches in lead zirconate titanate thin films
In undoped lead zirconate titanate films of 1–2 μm thick, domain walls move in clusters with a correlation length of approximately 0.5–2 μm. Band excitation piezoresponse force microscopy mapping of the piezoelectric nonlinearity revealed that niobium (Nb) doping increases the average concentration or mobility of domain walls without changing the cluster area of correlated domain wall motion. In contrast, manganese (Mn) doping reduces the contribution of mobile domain walls to the dielectric and piezoelectric responses without changing the cluster area for correlated motion. In both Nb and Mn doped films, the cluster area increases and the cluster density drops as the film thickness increases from 250 to 1250 nm. This is evident in spatial maps generated from the analysis of irreversible to reversible ratios of the Rayleigh coefficients.
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- Award ID(s):
- 2025439
- NSF-PAR ID:
- 10420049
- Date Published:
- Journal Name:
- Applied Physics Letters
- Volume:
- 122
- Issue:
- 13
- ISSN:
- 0003-6951
- Page Range / eLocation ID:
- 132906
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Uniformly acceptor doped Pb(Zr 0.48 Ti 0.52 )O 3 (PZT) films with 2 mol. % Mg or Fe prepared by chemical solution deposition exhibited decreased dielectric constants and remanent polarizations relative to undoped PZT. For highly accelerated lifetime testing (HALT) at 200 °C and an electric field of 300 kV/cm in the field up direction, the HALT lifetimes (t 50 ) for undoped, Mg-doped, and Fe-doped PZT films were shortened from 2.81 ± 0.1 to 0.21 ± 0.1 and 0.54 ± 0.04 h, respectively. Through thermally stimulated depolarization current measurement, significant [Formula: see text] electromigration was found in homogeneously Mg-doped PZT thin films, a major factor in their short HALT lifetime. Because the concentration of oxygen vacancies increases with uniform acceptor doping, the lifetime decreases. In contrast, when a thin layer of Mg-doped or Fe-doped PZT was deposited on undoped PZT or Nb-doped PZT (PNZT), the HALT lifetimes were longer than those of pure PZT or PNZT films. This confirms prior work on PNZT films with a Mn-doped top layer, demonstrating that the HALT lifetime increases for composite films when a layer with multivalent acceptors is present near the negative electrode during HALT. In that case, the compensating electrons are trapped, presumably on the multivalent acceptors, thus increasing the lifetime.more » « less
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1063/5.0149457
