This work represents a thorough investigation of the thermal conductivity (κ) in both thin film and bulk PbZr1-xTixO3 (PZT) across the compositional phase diagram. Given the technological importance of PZT as a superb piezoelectric and ferroelectric material in devices and systems impacting a wide array of industries, this research serves to fill the gap in knowledge regarding the thermal properties. The thermal conductivities of both thin film and bulk PZT are found to vary by a considerable margin as a function of composition x. Additionally, we observe a discontinuity in κ in the vicinity of the morphotropic phase boundary (MPB, x = 0.48) where there is a 20%-25% decrease in κ in our thin film data, similar to that found in literature data for bulk PZT. The comparison between bulk and thin film materials highlights the sensitivity of κ to size effects such as film thickness and grain size even in disordered alloy/solid-solution materials. A model for the thermal conductivity of PZT as a function of composition (κ (x)) is presented, which enables the application of the virtual crystal approximation for alloy-type material systems with very different crystals structures, resulting in differing temperature trends for κ. We show that in the case of crystalline solid-solutions where the thermal conductivity of one of the parent materials exhibits glass-like temperature trends the compositional dependence of thermal conductivity is relatively constant for most values of x. This is in stark contrast with the typical trends of thermal conductivity with x in alloys, where the thermal conductivity increases dramatically as the composition of the alloy or solid-solution approaches that of a pure parent materials (i.e., as x = 0 or 1).
The thermal conductivity of amorphous TaOx memristive films having variable oxygen content is measured using time domain thermoreflectance. Thermal transport is described by a two-part model where the electrical contribution is quantified via the Wiedemann-Franz relation and the vibrational contribution by the minimum thermal conductivity limit for amorphous solids. The vibrational contribution remains constant near 0.9 W/mK regardless of oxygen concentration, while the electrical contribution varies from 0 to 3.3 W/mK. Thus, the dominant thermal carrier in TaOx switches between vibrations and charge carriers and is controllable either by oxygen content during deposition, or dynamically by field-induced charge state migration.
Henriques, Alexandra; Graham, Joseph T.; Landsberger, Sheldon; Ihlefeld, Jon I.; Brennecka, Geoffrey L.; Brown, Donald W.; Forrester, Jennifer S.; Jones, Jacob L.
Piezoelectric and ferroelectric materials are useful as the active element in non-destructive monitoring devices for high-radiation areas. Here, crystallographic structural refinement (i.e., the Rietveld method) is used to quantify the type and extent of structural changes in PbZr0.5Ti0.5O3 after exposure to a 1 MeV equivalent neutron fluence of 1.7×1015 neutrons/cm2. The results showa measurable decrease in the occupancy of Pb and O due to irradiation, with O vacancies in the tetragonal phase being created preferentially on one of the two Osites. The results demonstrate a method by which the effects of radiation on crystallographic structure may be investigated.
Electric field-induced reversal of spontaneous polarization is the defining characteristic of a ferroelectric material, but the process(es) and mechanism(s) associated with the initial nucleation of reverse-polarity domains are poorly understood. This report describes studies carried out using phase field modeling of LiTaO3, a relatively simple prototype ferroelectric material, in order to explore the effects of either mechanical deformation or optically-induced free charges on nucleation and resulting domain configuration during field-induced polarization reversal. Conditions were selected to approximate as closely as feasible those of accompanying experimental work in order to provide not only support for the experimental work but also ensure that additional experimental validation of the simulations could be carried out in the future. Phase field simulations strongly support surface mechanical damage/deformation as effective for dramatically reducing the overall coercive field (Ec) via local field enhancements. Further, optically-nucleated polarization reversal appears to occur via stabilization of latent nuclei via the charge screening effects of free charges.
Density-functional theory calculations, ab-initio molecular dynamics, and the Kubo-Greenwood formula are applied to predict electrical conductivity in Ta2Ox (0 x 5) as a function of composition, phase, and temperature, where additional focus is given to various oxidation states of the O monovacancy (VOn; n=0,1+,2+). Our calculations of DC conductivity at 300K agree well with experimental measurements taken on Ta2Ox thin films and bulk Ta2O5 powder-sintered pellets, although simulation accuracy can be improved for the most insulating, stoichiometric compositions. Our conductivity calculations and further interrogation of the O-deficient Ta2O5 electronic structure provide further theoretical basis to substantiate VO0 as a donor dopant in Ta2O5 and other metal oxides. Furthermore, this dopant-like behavior appears specific to neutral VO cases in both Ta2O5 and TiO2 and was not observed in other oxidation states. This suggests that reduction and oxidation reactions may effectively act as donor activation and deactivation mechanisms, respectively, for VO0 in transition metal oxides.
Radiation hard nonvolatile random access memory (NVRAM) is a crucial component for DOE and DOD surveillance and defense applications. NVRAMs based upon ferroelectric materials (also known as FERAMs) are proven to work in radiation-rich environments and inherently require less power than many other NVRAM technologies. However, fabrication and integration challenges have led to state-of-the-art FERAMs still being fabricated using a 130nm process while competing phase-change memory (PRAM) has been demonstrated with a 20nm process. Use of block copolymer lithography is a promising approach to patterning at the sub-32nm scale, but is currently limited to self-assembly directly on Si or SiO{sub 2} layers. Successful integration of ferroelectrics with discrete and addressable features of {approx}15-20nm would represent a 100-fold improvement in areal memory density and would enable more highly integrated electronic devices required for systems advances. Towards this end, we have developed a technique that allows us to carry out block copolymer self-assembly directly on a huge variety of different materials and have investigated the fabrication, integration, and characterization of electroceramic materials - primarily focused on solution-derived ferroelectrics - with discrete features of {approx}20nm and below. Significant challenges remain before such techniques will be capable of fabricating fully integrated NVRAM devices, but the tools developed for this effort are already finding broader use. This report introduces the nanopatterned NVRAM device concept as a mechanism for motivating the subsequent studies, but the bulk of the document will focus on the platform and technology development.
Ferroelectric lead zirconate titanate (PZT) thin films are used for integrated capacitors, ferroelectric memory, and piezoelectric actuators. Solution deposition is routinely used to fabricate these thin films. During the solution deposition process, the precursor solutions are spin coated onto the substrate and then pyrolyzed to form an amorphous film. The amorphous film is then heated at a higher temperature (650-700 C) to crystallize the film into the desired perovskite phase. Phase purity is critical in achieving high ferroelectric properties. Moreover, due to the anisotropy in the structure and properties of PZT, it is desirable to control the texture obtained in these thin films. The heating rate during crystallization process is known to affect the sequence of phase evolution and texture obtained in these thin films. However, to date, a comprehensive understanding of how phase and texture evolution takes place is still lacking. To understand the effects of heating rate on phase and texture evolution, in-situ diffraction experiments during the crystallization of solution deposited PZT thin films were carried out at beamline 6-ID-B, Advanced Photon Source (APS). The high X-ray flux coupled with the sophisticated detectors available at the APS synchrotron source allow for in-situ characterization of phase and texture evolution at the high ramp rates that are commonly used during processing of PZT thin films. A PZT solution of nominal composition 52/48 (Zr/Ti) was spin coated onto a platinum-coated Si substrate (Pt//TiO{sub x}//SiO{sub 2}//Si). The films were crystallized using an infrared lamp, similar to a rapid thermal annealing furnace. The ramp rate was adjusted by controlling the voltage applied to the infrared lamp and increasing the voltage by a constant step with every acquisition. Four different ramp rates, ranging from {approx}1000 C/s to {approx}1 C/s, were investigated. The sample was aligned in grazing incidence to maximize the signal from the thin films. Successive diffraction patterns were acquired with a 1s acquisition time using a MAR SX-165 CCD detector during crystallization. The sample to detector distance and the tilt rotations of the detector were determined in Fit2D{copyright} by using Al{sub 2}O{sub 3} as the calibrant. These corrections were applied to the patterns when binning the data into radial (2{theta}) and azimuthal bins. The texture observed in the thin film was qualitatively analyzed by fitting the intensity peaks along the azimuthal direction with a gaussian profile function to obtain the integrated intensity of the peaks. Data analysis and peak fitting was done using the curve fitting toolbox in MATLAB{copyright}. A fluorite-type phase was observed to form before the perovskite phase for all ramp rates. PtxPb is a transient intermetallic formed due to the interaction of the thin film and the bottom electrode during crystallization. Ramp rate was observed to significantly affect the amount of PtxPb observed in the thin films during crystallization. Ramp rate was also observed to affect the final texture obtained in the thin films. These results will be discussed in the poster in view of the current understanding of these materials.
This report focuses on our recent advances in the fabrication and processing of barium strontium titanate (BST) thin films by chemical solution depositiion for next generation fuctional integrated capacitors. Projected trends for capacitors include increasing capacitance density, decreasing operating voltages, decreasing dielectric thickness and decreased process cost. Key to all these trends is the strong correlation of film phase evolution and resulting microstructure, it becomes possible to tailor the microstructure for specific applications. This interplay will be discussed in relation to the resulting temperature dependent dielectric response of the BST films.
This report focuses on our recent advances in the fabrication and processing of barium strontium titanate (BST) thin films by chemical solution deposition for next generation functional integrated capacitors. Projected trends for capacitors include increasing capacitance density, decreasing operating voltages, decreasing dielectric thickness and decreased process cost. Key to all these trends is the strong correlation of film phase evolution and resulting microstructure, it becomes possible to tailor the microstructure for specific applications. This interplay will be discussed in relation to the resulting temperature dependent dielectric response of the BST films.