Microstructural development in solution-derived PZT thin films

Author(s):  
T. J. Headley ◽  
B. A. Tuttle ◽  
J. A. Voigt ◽  
J. R. Michael

Lead zirconate titanate (PZT) thin films are of technological interest for a variety of electronic and optical applications such as nonvolatile memories, decoupling capacitors, infrared detectors, and optical storage media. Fabrication of PZT films by solution deposition techniques is attractive because of uniform, stoichiometric control at the molecular level, ease of processing, and both low capital investment and total cost. Control of phase evolution, microstructure, crystallite size and orientation, and ferroelectric domain assemblage during processing is essential to optimize electrical and/or optical properties of the films. Factors which play a major role in controlling these parameters are details of the solution chemistry and mixing, thermal processing, Pb stoichiometry, Zr/Ti ratio, and substrate characteristics. Electron microscopy techniques have been used extensively to correlate microstructural features with film processing parameters as will be emphasized in this presentation.As annealing temperature is increased, phase evolution in PZT thin films typically proceeds from amorphous to pyrochlore to the ferroelectric perovskite phase. Fine-grained pyrochlore crystallizes from the amorphous film at low annealing temperatures and also precedes crystallization of the perovskite phase at higher temperatures. There is evidence that the Zr/Ti stoichiometry influences the microstructure of the amorphous-to-pyrochlore transformation.

1993 ◽  
Vol 310 ◽  
Author(s):  
P. H. Ansari ◽  
A. Safari

AbstractFerroelectric lead zirconate titanate (PZT) films with a composition near the morphotropic phase boundary have been deposited by if magnetron sputtering on a Si substrate coated with silicon oxide, titanium, and platinum (Si/SiO2/Ti/Pt). Substrate temperature and oxygen partial pressure were changed during deposition to prepare films with controlled stoichiometry and perovskite structure. The effects of lead titanate (PT) as a buffer layer were investigated. Thin films of PT/PZT have a dielectric constant of 800 with a dissipation factor of 0.04 at 1 kHz. The remnant polarization of 8μC/cm2 and the coercive field of 50 kV/cm were measured. The effect of processing on the formation of perovskite phase and the electrical properties will be discussed.


1996 ◽  
Vol 11 (8) ◽  
pp. 2076-2084 ◽  
Author(s):  
M. J. Lefevre ◽  
J. S. Speck ◽  
R. W. Schwartz ◽  
D. Dimos ◽  
S. J. Lockwood

The role of precursor stoichiometry and local firing environment on the microstructural development of sol-gel derived lead zirconate titanate (PZT) thin films was investigated. Typically, excess Pb is added to films to compensate for PbO volatilization during heat treatment. Here, it is shown that the use of stoichiometric precursors with either a PbO atmosphere powder or a PbO overcoat during the crystallization heat treatment is an attractive and viable alternative method for control of film stoichiometry. Using these approaches, we have fabricated single phase perovskite thin films with microstructures and electrical properties (Pr ∼ 36 μC/cm2 and Ec ∼ 45 kV /cm) comparable to those of films using optimized solution chemistries and excess Pb additions. The potential advantage of increasing PbO partial pressure, or activity, during firing versus excess Pb additions is discussed from the standpoint of a proposed crystallization scenario based on the kinetic competition between Pb loss and the nucleation and growth rates of the perovskite phase.


1999 ◽  
Vol 596 ◽  
Author(s):  
Zhan-jie Wang ◽  
Ryutaro Maeda ◽  
Kaoru Kikuchi

AbstractLead zirconate titanate (PZT) thin films were fabricated by a three-step heat-treatment process which involves the addition of -10, 0 and 10 mol% excess Pb to the starting solution and spin coating onto Pt/Ti/SiO2/Si substrates. Crystalline phases as well as preferred orientations in PZT films were investigated by X-ray diffraction analysis (XRD). The microstructure and composition of the films were studied by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electron probe microanalysis (EPMA), respectively. The well-crystallized perovskite phase and the (100) preferred orientation were obtained by adding 10% excess Pb to the starting solution. It was found that PZT films to which 10% excess Pb was added had better electric properties. The remanent polarization and the coercive field of this film were 34.8 μC/cm2 and 41.7 kV/cm, while the dielectric constant and loss values measured at 1 kHz were approximately 1600 and 0.04, respectively. Dielectric and ferroelectric properties were correlated to the microstructure of the films.


1995 ◽  
Vol 10 (12) ◽  
pp. 3149-3159 ◽  
Author(s):  
Ellen M. Griswold ◽  
L. Weaver ◽  
M. Sayer ◽  
I.D. Calder

The crystallization kinetics of the pyrochlore to perovskite phase transformation in lead zirconate titanate (PZT) thin films have been analyzed using rapid thermal processing (RTP). Sol-gel PZT thin films, fabricated on platinum electrodes, were annealed at 550 °C to 650 °C with hold times ranging from 1 s to 5 min. Glancing angle x-ray diffraction (XRD) was used for depth profiling to identify the location of phases in the films. Transmission electron microscopy (TEM) provided information on grain structure, nucleation, and growth. The phase information was correlated to the ferroelectric and dielectric properties. The perovskite phase nucleated in the pyrochlore phase throughout the film thickness, and at 650 °C the transformation was complete in 15 s. Fast growing (100) PZT nucleated at the platinum and consumed a small-grained matrix until a columnar structure was obtained. A ramp rate of 100 °C/s was sufficiently fast to prevent transformation during heating and allowed the direct application of an Avrami model for transformation kinetics. An activation energy of 610 kJ/mol was determined.


1991 ◽  
Vol 74 (6) ◽  
pp. 1455-1458 ◽  
Author(s):  
Altaf H. Carim ◽  
Bruce A. Tuttle ◽  
Daniel H. Doughty ◽  
Sheri L. Martinez

1996 ◽  
Vol 441 ◽  
Author(s):  
Sung-Tae Kim ◽  
Hyun-Ho Kim ◽  
Moon-Yong Lee ◽  
Won-Jong Lee

AbstractPerovskite-phase lead zirconate titanate (PZT) thin films were fabricated at 4751C by the electron cyclotron resonance (ECR) plasma enhanced DC magnetron multi-target reactive sputtering method on Pt/Ti/SiO2/Si and Pt/SiO2/Si substrates. Stoichiometric perovskite PZT films were readily obtained on Pt/Ti/SiO2/Si substrates because Ti atoms which were out-diffused to the Pt surface facilitated Pb incorporation by forming lead titanate at the early stage of deposition process. Activation of oxygen by ECR plasma facilitated the oxidation reaction and Pb incorporation into the film. Thus perovskite-phase PZT can be obtained on the Pt/SiO2/Si substrate.


2006 ◽  
Vol 326-328 ◽  
pp. 613-616
Author(s):  
Dae Jin Yang ◽  
Seong Je Cho ◽  
Jong Oh Kim ◽  
Won Youl Choi

Lead zirconate titanate (Pb(Zr0.48Ti0.52)O3 or PZT) films were grown on platinized silicon wafers (Pt/SiO2/Si) by d.c. reactive sputtering method with multi targets. The Pb content of PZT films has been widely recognized as affecting not only the phase formation and microstructure but also the dielectric and ferroelectric properties. Pb content of PZT films was controlled by the variation of Pb target current. The relation between Pb content and Pb target current was expressed as y=0.89x-11.09. The x and y are Pb target current and Pb content, respectively. The pyrochlore phase was transformed to perovskite phase as Pb content was increased. This phase transformation improved the ferroelectric properties of PZT films. In PZT films with perovskite phase, fatigue properties were not improved with excess Pb content. Fatigue properties of PZT films began to be fatigued after 106 switching cycles and coincided with the typical PZT fatigue behavior. Excess Pb content (Pb vacancy) did not affect the fatigue properties of PZT films.


2012 ◽  
Vol 2012 ◽  
pp. 1-9
Author(s):  
B. S. Li

Lead zirconate titanate (PZT) thin films with the morphotropic phase boundary composition (Zr/Ti = 52/48) have been prepared using a modified diol-based sol-gel route by introducing 1–5 mol% barium titanate (BT) nanoseeds into the precursor solution on platinized silicon substrates (Pt/Ti/SiO2/Si). Macroscopic electric properties of PZT film with nanoparticle showed a significant improvement of ferroelectric properties. This work aims at the systematic study of the local switching polarization behavior during fatigue in PZT films with and without nanoparticles by using very recent developed scanning piezoelectric microscopy (SPM). We show that the local fatigue performance, which is characterized by variations of local piezoloop with electric cycles, is significantly improved by adding some nanoseeds. It has been verified by scanning electron microscope (SEM) that the film grain morphology changes from columnar to granular structure with the addition of the nanoseeds. On the other hand, the existence of PtxPb transition phase, which existed in interface at early crystallization stage of pure PZT thin film, deteriorates the property of the interface. These microstructures and the interfaces of these films significantly affect the electrons injection occurred on the interfaces. The domain wall pinning induced by injected electrons and the succeeding penetration into the films is discussed to explain the fatigue performance.


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