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Results for “Pyroelectricity”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Pyroelectric Heat Detection for Calibrated Measurement of Atomic Layer Deposition Reaction Heat

Atomic layer deposition (ALD) precursors and processes have been identified that enable the deposition of materials that span the periodic table. However, the detailed mechanisms, kinetics, thermodynamics, and complexities of even the most well-studied ALD half-reactions remain insufficiently resolved experimentally to test present computational hypotheses. In this work, a pyroelectric calorimeter is designed, implemented, calibrated, and electrically modeled to enable quantitative ALD reaction heat detection. The operation and response of three ALD calorimeter designs were evaluated for use as absolute ALD half-reaction heat detectors. The most effective design was calibrated in situ before being utilized to measure the heat generated by the reaction of trimethylaluminum with a hydroxylated alumina surface to produce 96 μJ/cm 2 over a reaction time of ~30 ms. With thermal and temporal resolutions down to 0.1 μJ/cm 2 and 50 ns, respectively, this sensitive and ultrafast probe is poised to improve our fundamental understanding of numerous ALD reaction mechanisms through quantitative comparison with first-principles computation predictions.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Capabilities of GaN/AlN/GaN structures as high-intensity pyroelectric laser sensors

The use of transparent Al{sub 2}O{sub 3}/GaN/AlN/GaN structures as pyrometric sensors for measuring the parameters of high-intensity laser pulses is proposed. The peculiarities of the employment of such sensors in laser fusion facilities are analysed. Post-pulse distributions of the absorbed energy density are obtained for various parameters of both GaN layers. The local maxima of these distributions are minimised by varying the ratio of donor concentration and the ratio of their thicknesses under the condition of invariance of the total absorbed energy. The optimal structure configuration is established in terms of reducing the possible negative effect of laser impact on the pyroelectric coefficient stability. (paper)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Wake-up and fatigue mechanisms in ferroelectric Hf 0.5 Zr 0.5 O 2 films with symmetric RuO 2 electrodes

In this work, the mechanisms leading to wake-up and fatigue in ferroelectric hafnium zirconium oxide thin film devices with symmetric RuO 2 electrodes are investigated via polarization, relative permittivity, dielectric nonlinearity, pyroelectric coefficient, and microfocus X-ray diffraction (XRD) measurements. The devices are observed to wake-up for up to 10 3 bipolar pulsed field cycles, after which fatigue occurs with the polarization approaching zero following 10 8 cycles. Wake-up is accompanied by a decrease in both high-field permittivity and hysteresis loop pinching and an increase in pyroelectric coefficient, indicating that the wake-up process involves a combination of transformations from the tetragonal to the orthorhombic phase and domain depinning from defect redistribution. Fatigue is observed to coincide with an increase in irreversible domain wall motion and a decrease in pyroelectric coefficient. Finite pyroelectric coefficients are measured on fully fatigued devices, indicating that domain pinning is a strong contributor to fatigue and that fatigued devices contain domain structures that are unable to switch under the fields applied for measurement. Microfocus XRD patterns measured on each device reveal that the phase constitution is qualitatively unaffected by the field cycling and resultant polarization fatigue. This data indicates that the wake-up process has contributions from both phase transformations and domain depinning, whereas the fatigue process is driven primarily by domain pinning, and the near-zero measured switchable polarization is actually a poled device with immobile domains. These observations provide insight into the physical changes occurring during field cycling of HfO 2 -based ferroelectrics while examining a possible oxide electrode material for silicon CMOS device implementation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

High Efficiency Waste Heat Harvesting Using Novel Thermal Oscillators

The aim of this project was to enable practical energy generation from waste heat using pyroelectric (PE) materials with unprecedented efficiency. This aim was accomplished by engineering novel heat switches that overcome the current roadblock to pyroelectric energy harvesting. The heat switches produce a sustain temporal temperature differences from a constant flux heat source. Pyroelectric materials produce transient voltages in response to this generated temperature oscillation. The project solved the inability to generate sustained temperature cycles by utilizing LCEs to achieve passive thermal switching, or EDH of thermal fluid to actively bridging/de-bridging between heat source and pyroelectric layer.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2020

Chapter 3 - Harvesting Thermal Energy with Ferroelectric Materials

Thermal energy is considered the ubiquitous form of energy as all other forms of energy ultimately degrade to thermal energy. Thermal to electrical energy conversion is currently an important method for electricity generation. The traditional power cycles, however, become technically and economically unviable when heat source temperature reduces below 100 °C. Thermal energy harvesting has been proposed as a viable alternative for low-grade thermal to electrical energy conversion. Thermal energy harvesting is a method of generating electricity using temperature-induced variations in material properties. It is particularly useful when the heat sources are available free-of-cost, either in the form of natural heat or waste heat. While there are several thermal energy harvesting techniques, pyroelectricity is the most promising as it can be used in situations where spatial thermal gradients are difficult to establish or the temperature of the heat source is changing. Despite the fact that the pyroelectric effect in ferroelectric materials has been known for past several decades, thermal energy harvesting using ferroelectric materials has not been much explored in the literature. In this chapter, we would explore various aspects of thermal energy harvesting using ferroelectric materials. We have first established the physics behind ferroelectricity, then provided a detailed description on ferroelectric thermal energy harvesting, discussed various ferroelectric thermodynamic cycles and devices proposed in the literature, and finally described various other emerging applications of ferroelectricity.

DIRECT ENERGY CONVERSION,MATERIALS SCIENCE,OTHER I↗
DOE OSTI2021

Broad Distribution of Local Polar States Generates Large Electrothermal Properties in Pb-Free Relaxor Ferroelectrics

Electrothermal energy conversion provides attractive solutions for global energy management, such as energy harvesting from waste heat using pyroelectric energy conversion (PEC) and efficient cooling of portable electronics or data servers using the electrocaloric effect. Relaxor ferroelectrics are attractive for electrothermal energy conversion because of their large pyroelectric coefficients over a wide temperature range. Although Pb-based relaxors are well-known, toxicity concerns have mandated the intense search for Pb-free alternatives. Here, we engineered (Ba,Ca)TiO 3 -based relaxors based on a multisite doping strategy, which show promising electrothermal performance, viz. a maximum PEC efficiency of 14% and electrocaloric refrigeration capacity of 115 J/kg. Using local-scale structural analysis, we provide an atomistic model for large electrothermal properties in the newly designed Pb-free ferroelectrics, whereby a temperature-independent continuous distribution of cation displacement directions creates easy pathways for microscopic polarization reorientation. This research provides key structural insight for future atomic-scale engineering of environmentally sustainable ferroelectrics in energy applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

High Entropy Oxide Relaxor Ferroelectrics

Relaxor ferroelectrics are important in technological applications due to strong electromechanical response, energy storage capacity, electrocaloric effect, and pyroelectric energy conversion properties. Current efforts to discover and design materials in this class generally rely on substitutional doping as slight changes to local compositional order can significantly affect the Curie temperature, morphotropic phase boundary, and electromechanical responses. In this work, we demonstrate that moving to the strong limit of compositional complexity in an ABO 3 perovskite allows stabilization of relaxor responses that do not rely on a single narrow phase transition region. Entropy-assisted synthesis approaches are utilized to synthesize single-crystal Ba(Ti 0.2 Sn 0.2 Zr 0.2 Hf 0.2 Nb 0.2 )O 3 [Ba(5B)O] films. The high levels of configurational disorder present in this system are found to influence dielectric relaxation, phase transitions, nanopolar domain formation, and Curie temperature. Temperature-dependent dielectric, Raman spectroscopy, and second-harmonic generation measurements reveal multiple phase transitions, a high Curie temperature of 570 K, and the relaxor ferroelectric nature of Ba(5B)O films. The first-principles theory calculations are used to predict possible combinations of cations to design relaxor ferroelectrics and quantify the relative feasibility of synthesizing these highly disordered single-phase perovskite systems. Further, the ability to stabilize single-phase perovskites with various cations on the B-sites offers possibilities for designing high-performance relaxor ferroelectric materials for piezoelectric, pyroelectric, and electrocaloric applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Resolving the Heat of Trimethylaluminum and Water Atomic Layer Deposition Half-Reactions

We report that atomic layer deposition (ALD) is a surface synthesis technique that is characterized by self-limiting reactions between gas-phase precursors and a solid substrate. Although ALD processes have been demonstrated that span the periodic table, a greater understanding of the surface chemistry that affords ALD is necessary to enable greater precision, including area- and site-selective growth. We offer new insight into the thermodynamics and kinetics of the trimethylaluminum (TMA) and H 2 O ALD half-reactions with calibrated and time-resolved in situ pyroelectric calorimetry. The half-reactions produce 3.46 and 2.76 eV/Al heat, respectively, which is greater than the heat predicted by computational models based on crystalline Al 2 O 3 substrates and closely aligned with the heat predicted by standard heats of formation. The pyroelectric thin-film calorimeter offers submilisecond temporal resolution that uniquely and clearly resolves precursor delivery and reaction kinetics. Both half-reactions are observed to exhibit multiple kinetic rates, with average TMA half-reaction rates at least 2 orders of magnitude faster than the H 2 O half-reaction kinetics. Comparing the experimental heat with published computational literature and additional first-principles modeling highlights the need to refine our models and mechanistic understanding of even the most ubiquitous ALD reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Atomic lift-off of epitaxial membranes for cooling-free infrared detection

Recent breakthroughs in ultrathin, single-crystalline, freestanding complex oxide systems have sparked industry interest in their potential for next-generation commercial devices. However, the mass production of these ultrathin complex oxide membranes has been hindered by the challenging requirement of inserting an artificial release layer between the epilayers and substrates. Here we introduce a technique that achieves atomic precision lift-off of ultrathin membranes without artificial release layers to facilitate the high-throughput production of scalable, ultrathin, freestanding perovskite systems. Leveraging both theoretical insights and empirical evidence, we have identified the pivotal role of lead in weakening the interface. This insight has led to the creation of a universal exfoliation strategy that enables the production of diverse ultrathin perovskite membranes less than 10 nm. Our pyroelectric membranes demonstrate a record-high pyroelectric coefficient of 1.76 × 10 −2 C m −2 K −1 , attributed to their exceptionally low thickness and freestanding nature. Moreover, this method offers an approach to manufacturing cooling-free detectors that can cover the full far-infrared spectrum, marking a notable advancement in detector technology.

nanoscale materials↗
DOE OSTI2020

Relaxor behavior and electrothermal properties of Sn- and Nb-modified (Ba,Ca)TiO 3 Pb-free ferroelectric

Relaxor ferroelectrics have drawn attention for possible applications in solid-state cooling and thermal energy harvesting, owing to their electrothermal energy conversion properties. Here, we have synthesized and characterized the structure–property correlations of a new Sn- and Nb-doped (Ba,Ca)TiO 3 relaxor ferroelectric with large pyroelectric and electrocaloric effects over a broad temperature range. We observed two peaks for the temperature-dependent pyroelectric coefficient: (i) -(∂P/∂T) ~ 563 µC/(m 2 K) at T~ 270 K and (ii) -(∂P/∂T) ~ 1021 µC/(m 2 K) at T~ 320 K. In addition, a broad peak for electrocaloric temperature change is observed near 320 K with a relative cooling power of ~17 J/kg. These properties could be correlated to structural changes observed using X-ray diffraction at two different temperature ranges in the material. Analysis of high-energy X-ray scattering and specific heat capacity data revealed a transition from the cubic to tetragonal phase near T m ~ 320 K, whereas an additional increase in the tetragonality (c/a) of the polar phase is observed below T s ~ 270 K.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Giant magnetostriction and nonsaturating electric polarization up to 60 T in the polar magnet $\mathrm{CaBaCo_4O_7}$

Giant magnetostriction in insulating magnetic materials is highly required for applications but is rarely observed. Here we show that giant magnetostriction (> 1500 ppm) can be achieved in an insulating transition metal oxide CaBaCo 4 O 7 where the ferrimagnetic ordering at T c ~ 62K is associated with a huge change in the lattice. Moreover, because this material is pyroelectric with a nonswitchable electric polarization (P), the giant magnetostriction results in a pronounced magnetoelectric effect—a huge change of electric polarization (ΔP ~ 1.6μC/cm 2 ) in response to the applied magnetic field up to 60 T. Geometric frustration as well as the orbital instability of Co 2+ /Co 3+ ions is believed to play a crucial role in the giant magnetostriction. Here our study provides insights on how to achieve both giant magnetostriction and pronounced magnetoelectric effect in insulating transition metal oxides.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Piezosuperconductivity: Novel effects in noncentrosymmetric superconductors

Here we study effects in noncentrosymmetric superconductors arising from their unique coupling of Cooper-pair condensate and elasticity. We show that although the much discussed Lifshitz coupling is not observable in a uniform bulk state, it strikingly endows dislocations with a fractional magnetic flux. We also predict a generation of voltage-free strain by a DC current in a P- and T-breaking Josephson junction. Viewing superconductors through the lens of higher-form symmetries we identify the Lifshitz coupling as a chemical potential for the approximately conserved winding number, drawing an analogy with pyroelectric insulators.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Resolving the Heat Generated from ZrO 2 Atomic Layer Deposition Surface Reactions

Abstract In situ pyroelectric calorimetry and spectroscopic ellipsometry were used to investigate surface reactions in atomic layer deposition (ALD) of zirconium oxide (ZrO 2 ). Calibrated and time‐resolved in situ ALD calorimetry provides new insights into the thermodynamics and kinetics of saturating surface reactions for tetrakis(dimethylamino)zirconium(IV) (TDMAZr) and water. The net ALD reaction heat ranged from 0.197 mJ cm −2 at 76 °C to 0.155 mJ cm −2 at 158 °C, corresponding to an average of 4.0 eV/Zr at all temperatures. A temperature dependence for reaction kinetics was not resolved over the range investigated. The temperature dependence of net reaction heat and distribution among metalorganic and oxygen source exposure is attributed to factors including growth rate, equilibrium surface hydroxylation, and the extent of the reaction. ZrO 2 ‐forming surface reactions were investigated computationally using DFT methods to better understand the influence of surface hydration on reaction thermodynamics.

Bielinski, Ashley R.↗
DOE OSTI2023

Resolving the Heat Generated from ZrO 2 Atomic Layer Deposition Surface Reactions

Abstract In situ pyroelectric calorimetry and spectroscopic ellipsometry were used to investigate surface reactions in atomic layer deposition (ALD) of zirconium oxide (ZrO 2 ). Calibrated and time‐resolved in situ ALD calorimetry provides new insights into the thermodynamics and kinetics of saturating surface reactions for tetrakis(dimethylamino)zirconium(IV) (TDMAZr) and water. The net ALD reaction heat ranged from 0.197 mJ cm −2 at 76 °C to 0.155 mJ cm −2 at 158 °C, corresponding to an average of 4.0 eV/Zr at all temperatures. A temperature dependence for reaction kinetics was not resolved over the range investigated. The temperature dependence of net reaction heat and distribution among metalorganic and oxygen source exposure is attributed to factors including growth rate, equilibrium surface hydroxylation, and the extent of the reaction. ZrO 2 ‐forming surface reactions were investigated computationally using DFT methods to better understand the influence of surface hydration on reaction thermodynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗