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 Title: Evolution of local structure and stress development during thermal treatment of sol-gel-derived PZT-based thin layers Author(s): Sengupta, Samit Sushil Doctoral Committee Chair(s): Payne, David A. Department / Program: Materials Science Engineering Discipline: Materials Science Engineering Degree Granting Institution: University of Illinois at Urbana-Champaign Degree: Ph.D. Genre: Dissertation Subject(s): Engineering, Materials Science Abstract: Significant progress has been made in recent years on the deposition of ferroelectric thin layers by sol-gel processing. However, to sustain further improvements in the technique necessary for widespread applications, a systematic approach to the study of physical, chemical and structural changes that occur during transformation from the as-deposited state to the desired perovskite phase must be undertaken. In view of the need for a fundamental understanding of structure-processing relationships in these systems, this thesis investigates variations in local structure and network development for sol-gel derived precursors in the lead zirconate titanate (PZT) system as a function of heat treatment conditions.Structural studies were based on extended x-ray absorption fine structure (EXAFS) analysis of gels and thin layers. Consolidation of the thin layer network was monitored by in situ ellipsometry and thermal analysis techniques. The resulting constrained shrinkage for the deposited layers produced large stresses (up to 180 MPa), which were determined by wafer bending measurements.EXAFS measurements for partially heat-treated PZT gels are reported. After gels were dried and pyrolyzed, the amorphous structure was determined from results obtained from the titanium and zirconium K-edges and the lead L$\rm\sb{III}$-edge. For lead titanate (PT) and PZT53/47 gels, the results indicated the formation of separate TiO$\sb6$ and ZrO$\sb6$ units linked via corner-sharing oxygen atoms, with Pb in random positions. For lead zirconate (PZ) gels, both Zr-O-Pb and Zr-O-Zr linkages were possible. These findings indicate heterogeneity at the molecular level and nanoscale.Partially heat-treated thin layers of lead titanate deposited on polycrystalline alumina substrates were heat treated under various conditions to examine the evolution of the crystalline phase. Structural ordering was initiated by a progressive enhancement in the Pb-O coordination number and increased occupancy of Pb in the second shell of Ti, with a corresponding breakdown in the Ti-Ti second neighbor ordering. However, crystallization preceded complete development of the short-range order characteristic of the tetragonal perovskite unit.Densification of PZT thin layers spin-coated on silicon was monitored by shrinkage and optical measurements. With increasing Zr content, the net consolidation was greater and occurred over a wider temperature range. These differences were related to differences in the structure of the as-hydrolyzed precursors. Most of the total shrinkage (e.g., 40-45% linear shrinkage) on heating to 500$\sp\circ$C occurred during drying and pyrolysis, which resulted in large tensile stress ($\sim$150MPa). Subsequent stress behavior was primarily governed by the thermal expansion mismatch between the substrate and the coating.Stress development for multideposited PT coatings was determined by the structure of the layer on which the coating was being deposited and heat treated. Progressive crystallization of the layer induced a change in the thermal expansion coefficient, thereby initiating a change in the stress state from tensile to compressive. The observed behavior is discussed in terms of nucleation mechanisms at the multilayer interfaces and within the coating as a whole.This study has demonstrated the importance of identifying structural pathways and developing a basic understanding of the densification behavior in sol-gel derived materials as a function of thermal processing conditions. The findings of this research work should aid in developing suitable experimental procedures for future processing of gel-derived thin layers. Issue Date: 1996 Type: Text Language: English URI: http://hdl.handle.net/2142/21934 ISBN: 9780591199925 Rights Information: Copyright 1996 Sengupta, Samit Sushil Date Available in IDEALS: 2011-05-07 Identifier in Online Catalog: AAI9712435 OCLC Identifier: (UMI)AAI9712435
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