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At least 19 records

Development of improved pyroelectric detectors; Literature survey of pyroelectric materials and their characteristics

The object of this program is to improve the detectivity of the pyroelectric detector with the ultimate goal of operation at or near the temperature-noise limit. Two general areas of investigation are undertaken. The first is to improve responsivity through the use of new materials. The second is directed toward reduction of noise and will be effected with improved field effect transistor characteristics, and improved electroding of the pyroelectric material. The search for new materials has begun with a review of the literature on pyroelectric materials in several languages. The compiled data includes an extensive list of references. From this, several materials have already been selected for investigation. FETs are being obtained from various manufacturers, evaluated, and selected units will be tested with pyroelectric elements as complete detectors.

Weiner, S.↗

Development of improved pyroelectric detectors. Measurements of pyroelectric material characteristics and FET characteristics

Research was undertaken to improve the detectivity of the pyroelectric detector with the ultimate goal of operation at or near the temperature-noise limit. Two general areas of investigation were undertaken: (1) to improve responsivity through the use of new materials; and (2) to reduce noise through improved field effect transistor characteristics, and improved electroding of the pyroelectric material. FET's are being obtained from various manufacturers, evaulated, and selected units tested for evaluation of characteristics critical to their use as preamplifiers with pyroelectric detectors.

Weiner, S.↗

Development of improved pyroelectric detectors: Measurements of pyroelectric material characteristics and FET characteristics

The object of this program is to improve the detectivity of the pyroelectric detector with the ultimate goal of operation at or near the temperature noise limit. Two general areas of investigation are undertaken. The first is to improve responsivity through the use of new materials. The second is directed toward reduction of noise and will be effected with improved field effect transistor characteristics, and improved electroding of the pyroelectric material. The review of the literature on pyroelectric materials continues. From this, several materials have already been selected for investigation, and several were tested.

Weiner, S.↗

Surface Pyroelectricity in Cubic SrTiO 3

Symmetry-imposed restrictions on the number of available pyroelectric and piezoelectric materials remain a major limitation as 22 out of 32 crystallographic material classes exhibit neither pyroelectricity nor piezoelectricity. Yet, by breaking the lattice symmetry it is possible to circumvent this limitation. Here, using a unique technique for measuring transient currents upon rapid heating, direct experimental evidence is provided that despite the fact that bulk SrTiO 3 is not pyroelectric, the (100) surface of TiO 2 -terminated SrTiO 3 is intrinsically pyroelectric at room temperature. The pyroelectric layer is found to be ≈1 nm thick and, surprisingly, its polarization is comparable with that of strongly polar materials such as BaTiO 3 . The pyroelectric effect can be tuned ON/OFF by the formation or removal of a nanometric SiO 2 layer. Using density functional theory, the pyroelectricity is found to be a result of polar surface relaxation, which can be suppressed by varying the lattice symmetry breaking using a SiO 2 capping layer. The observation of pyroelectricity emerging at the SrTiO 3 surface also implies that it is intrinsically piezoelectric. Furthermore, these findings may pave the way for observing and tailoring piezo- and pyroelectricity in any material through appropriate breaking of symmetry at surfaces and artificial nanostructures such as heterointerfaces and superlattices.

30 DIRECT ENERGY CONVERSION↗

Origin of Pyroelectricity in Ferroelectric HfO 2

The pyroelectric response of materials is a promising phenomenon that is used in many applications. In this paper, we report first-principles lattice dynamics and ab initio molecular dynamics calculations to investigate the mechanisms of the pyroelectric effect in the Pca2 1 orthorhombic phase of HfO 2 ; this is an emerging pyroelectric material with promising technological applications. With first-principles lattice dynamics calculations, we demonstrate a large pyroelectric response that is intrinsic to the pure Pca21 orthorhombic phase. Unlike most conventional ferroelectric pyroelectrics, such large pyroelectricity arises unexpectedly from the secondary effect (induced by the negative longitudinal piezoelectric effect) that has not received due attention. Ab initio molecular dynamics simulations further demonstrate a giant pyroelectric response that is associated with an orthorhombic (polar) to tetragonal (nonpolar) structural phase transition. Upon the incorporation of Si dopants with increasing dopant concentrations, the phase transition persists, but occurs at reduced temperatures with enhanced pyroelectric responses. The present work highlights the importance of the secondary pyroelectric effect responsible for the pyroelectricity in HfO 2 and its promising potential for device applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Manipulating electron redistribution to achieve electronic pyroelectricity in molecular [FeCo] crystals

Pyroelectricity plays a crucial role in modern sensors and energy conversion devices. However, obtaining materials with large and nearly constant pyroelectric coefficients over a wide temperature range for practical uses remains a formidable challenge. Attempting to discover a solution to this obstacle, we combined molecular design of labile electronic structure with the crystal engineering of the molecular orientation in lattice. This combination results in electronic pyroelectricity of purely molecular origin. Here, we report a polar crystal of an [FeCo] dinuclear complex exhibiting a peculiar pyroelectric behavior (a substantial sharp pyroelectric current peak and an unusual continuous pyroelectric current at higher temperatures) which is caused by a combination of Fe spin crossover (SCO) and electron transfer between the high-spin Fe ion and redox-active ligand, namely valence tautomerism (VT). As a result, temperature dependence of the pyroelectric behavior reported here is opposite from conventional ferroelectrics and originates from a transition between three distinct electronic structures. The obtained pyroelectric coefficient is comparable to that of polyvinylidene difluoride at room temperature.

36 MATERIALS SCIENCE↗

Quantifying Intrinsic, Extrinsic, Dielectric, and Secondary Pyroelectric Responses in PbZr 1–x Ti x O 3 Thin Films

Applications such as solid-state waste-heat energy conversion, infrared sensing, and thermally-driven electron emission rely on pyroelectric materials (a subclass of dielectric piezoelectrics) which exhibit temperature-dependent changes in polarization. Although enhanced dielectric and piezoelectric responses are typically found at polarization instabilities such as temperature- and chemically induced phase boundaries, large pyroelectric effects have been primarily limited in study to temperature-induced phase boundaries. Here in this paper, we directly identify the magnitude and sign of the intrinsic, extrinsic, dielectric, and secondary pyroelectric contributions to the total pyroelectric response as a function of chemistry in thin films of the canonical ferroelectric PbZr$_{1-x}$Ti$_x$O$_3$ (x = 0.40, 0.48, 0.60, and 0.80) across the morphotropic phase boundary. Using phase-sensitive frequency and applied dc-bias methods, the various pyroelectric contributions were measured. It is found that the total pyroelectric response decreases systematically as one moves from higher to lower titanium contents. This arises from a combination of decreasing intrinsic response (-232 to -97 μC m$^{-2}$ K$^{-1}$) and a sign inversion (+33 to -17 μC m$^{-2}$ K$^{-1}$)) of the extrinsic contribution upon crossing the morphotropic phase boundary. Additionally, the measured secondary and dielectric contributions span between -70 and -29 and 10-115 μC m$^{-2}$K$^{-1}$) under applied fields, respectively, following closely trends in the piezoelectric and dielectric susceptibility. These findings and methodologies provide novel insights into the understudied realm of pyroelectric response.

36 MATERIALS SCIENCE↗

Pyroelectricity of Lead Sulfide (PbS) Quantum Dot Films Induced by Janus-Ligand Shells

Asymmetry is an essential property to control. To do that in nanocrystalline systems we have developed methods to produce Janus-ligand shells on otherwise symmetric PbS quantum dots (QDs). In this work, we demonstrate that control by constructing a system that exhibits pyroelectricity built from spherical PbS QDs. We observed a pyroelectric current in two different configurations. In one configuration, the QDs are self-assembled into close-packed arrays while in the second configuration, the QDs are dispersed into an electro-inactive polymer, polydimethylsiloxane. Both exhibit a pyroelectric response. In the first configuration we estimate a lower limit of the pyroelectric coefficient to be 1.97 × 10 -7 C/m 2 K, which is likely limited by the degree of QD alignment during film formation but is already on par with common pyroelectric systems. Compared with inorganic ceramic-like and polymeric pyroelectric materials, pyroelectric films self-assembled from polar QDs are easier to prepare, responsive to light with different energies based on QD exciton energy, and the polarization of each QD could be easily tuned by constructing different Janus-ligand shells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhanced pyroelectric properties of Bi 1-x La x FeO 3 thin films

There is growing interest in the study of thin-film pyroelectric materials because of their potential for high performance thermal-energy conversion, thermal sensing, and beyond. Electrothermal susceptibilities, such as pyroelectricity, are known to be enhanced in proximity to polar instabilities, and this is conventionally accomplished by positioning the material close to a temperature-driven ferroelectric-to-paraelectric phase transition. The high Curie temperature (T C ) for many ferroelectrics, however, limits the utility of these materials at room-temperature. Here, the nature of pyroelectric response in thin films of the widely studied multiferroic Bi 1-x La x FeO 3 (x = 0-0.45) is probed. While BiFeO 3 itself has a high T C , lanthanum substitution results in a chemically induced lowering of the ferroelectric-to-paraelectric and structural-phase transition. The effect of isovalent lanthanum substitution on the structural, dielectric, ferroelectric, and pyroelectric response is investigated using reciprocal-space-mapping studies; field-, frequency-, and temperature-dependent electrical measurements; and phase-sensitive pyroelectric measurements, respectively. While BiFeO 3 itself has a rather small pyroelectric coefficient at room temperature (~-40 μC/m 2 K), 15% lanthanum substitution results in an enhancement of the pyroelectric coefficient by 100% which is found to arise from a systematic lowering of T C .

36 MATERIALS SCIENCE↗

Pyroelectric conversion in space: A conceptual design study

Pyroelectric conversion is potentially a very lightweight means of providing electrical power generation in space. Two conceptualized systems approaches for the direct conversion of heat (from sunlight) into electrical energy using the pyroelectric effect of a new class of polar polymers were evaluated. Both of the approaches involved large area thin sheets of plastic which are thermally cycled by radiative input and output of thermal energy. The systems studied are expected to eventually achieve efficiencies of the order of 8% and may deliver as much as one half kilowatt per kilogram. In addition to potentially very high specific power, the pyroelectric conversion approaches outlined appear to offer low cost per watt in the form of an easily deployed, flexible, strong, electrically ""self-healing'', and high voltage sheet. This study assessed several potential problems such as plasma interactions and radiation degradation and suggests approaches to overcome them. The fundamental technological issues for space pyroelectric conversion are: (1) demonstration of the conversion cycle with the proposed class of polymers, (2) achievement of improved dielectric strength of the material, (3) demonstration of acceptable plasma power losses for low altitude, and (4) establishment of reasonable lifetime for the pyroelectric material in the space environment. Recommendations include an experimental demonstration of the pyroelectric conversion cycle followed by studies to improve the dielectric strength of the polymer and basic studies to discover additional pyroelectric materials.

Olsen, R. B.↗

Polarization-dependent electrocaloric and pyroelectric effects in ferroelectric BaTiO 3 thin films

In this paper we examine the influence of controllable polarization reversal and built-in electric fields on pyroelectric and electrocaloric effects in a BaTiO 3 thin film using a modified indirect method. We find that the magnitude of the sample's change in polarization with temperature is sensitive to the degree of polarization reversal. The pyroelectric response is small at low fractions of switched polarization and grows larger by several factors as larger fractions of polarization are reversed. This polarization reversal-sensitive pyroelectric behavior is the result of an internal built-in field, which has the effect of destabilizing low fractions of switched polarization and producing diminished pyroelectric effect. Greater fractions of switched polarization are more stable against backswitching and permit a larger pyroelectric response. Our findings highlight a characterization method for polarization-dependent pyroelectric effects in ferroelectric thin films, where built-in field effects are also present.

36 MATERIALS SCIENCE↗

Virus‐Based Pyroelectricity

Abstract The first observation of heat‐induced electrical potential generation on a virus and its detection through pyroelectricity are presented. Specifically, the authors investigate the pyroelectric properties of the M13 phage, which possesses inherent dipole structures derived from the noncentrosymmetric arrangement of the major coat protein (pVIII) with an α‐helical conformation. Unidirectional polarization of the phage is achieved through genetic engineering of the tail protein (pIII) and template‐assisted self‐assembly techniques. By modifying the pVIII proteins with varying numbers of glutamate residues, the structure‐dependent tunable pyroelectric properties of the phage are explored. The most polarized phage exhibits a pyroelectric coefficient of 0.13 µC m −2 °C −1 . Computational modeling and circular dichroism (CD) spectroscopy analysis confirm that the unfolding of α‐helices within the pVIII proteins leads to changes in phage polarization upon heating. Moreover, the phage is genetically modified to enable its pyroelectric function in diverse chemical environments. This phage‐based approach not only provides valuable insights into bio‐pyroelectricity but also opens up new opportunities for the detection of various viral particles. Furthermore, it holds great potential for the development of novel biomaterials for future applications in biosensors and bioelectric materials.

Kim, Han↗

Neutron generation using pyroelectric crystals

A method for producing a neutrons includes producing a voltage of negative polarity of at least −100 keV on a surface of a deuterated or tritiated target in response to a temperature change of a pyroelectric crystal of less than about 40° C., the pyroelectric crystal having the deuterated or tritiated target coupled thereto, pulsing a deuterium ion source to produce a deuterium ion beam, accelerating the deuterium ion beam to the deuterated or tritiated target, and directing the ion beam onto the deuterated or tritiated target to make neutrons using at least one element of the following: a voltage of the pyroelectric crystal and a high gradient insulator (HGI) surrounding the pyroelectric crystal. The accelerating of the deuterium ion beam is achieved by using an ion accelerating mechanism comprising a pyroelectric stack accelerator having a first thermal altering mechanism for changing a temperature of the pyroelectric stack accelerator.

Tang, Vincent↗

Electronic detection of ultra-heavy nuclei by pyroelectric materials

A recent prediction by the authors that pyroelectric materials may be capable of detecting ultra-heavy nuclei has been confirmed. Charge pulse signals from pyroelectric crystals of lithium tantalate exposed to Au ions and a pulsed beam of Ni-58 ions, and from pyroelectric films of polyvinylidene fluoride exposed to a pulsed beam of Ni-58 ions, have been measured using pulse electronics with time constants in the microsecond range. These studies show that pyroelectric materials, in general, are capable of detecting incident nuclei having very high mass and charge. In particular, pyroelectric polymers, such as polyvinylidene fluoride, are readily available as inexpensive flexible films. This new class of charged particle detector could eventually find applications in large-area experiments for detection and trajectory determination of low-energy, ultra-heavy nuclei.

Simpson, J. A.↗

Effect of space exposure of pyroelectric infrared detectors

Pyroelectric detectors are one of many different types of infrared radiation detectors. The pyroelectric detectors are of interest for long term space use because they do not require cooling during operation. Also, they can detect at very long wavelengths and they have a relatively flat spectral response. A disadvantage is that the radiation must be chopped in order to be detected by a pyroelectric detector. The objective was to determine the effects of launch and space exposure on the performance of commercially available pyroelectric detectors. The approach was to measure certain detector parameters before and after flight and try to determine the amount and cause of the degradation. The experiment was passive: no data was taken during flight. It is concluded that lithium-tantalate and strontium-barium-niobate are suitable materials for pyroelectric detectors for long term space applications.

Robertson, James B.↗

Polymer-Ceramic Composite Materials for Pyroelectric Infrared Detectors: An Overview

Ferroelectrics:Polymer composites can be considered an established substitute for conventional electroceramics and ferroelectric polymers. The composites have a unique blend of polymeric properties such as mechanical flexibility, high strength, formability, and low cost, with the high electro-active properties of ceramic materials. They have attracted considerable interest because of their potential use in pyroelectric infrared detecting devices and piezoelectric transducers. These flexible sensors and transducers may eventually be useful for their health monitoring applications for NASA crew launch vehicles and crew exploration vehicles being developed. In the light of many technologically important applications in this field, it is worthwhile to present an overview of the pyroelectric infrared detector theory, models to predict dielectric behavior and pyroelectric coefficient, and the concept of connectivity and fabrication techniques of biphasic composites. An elaborate review of Pyroelectric-Polymer composite materials investigated to date for their potential use in pyroelectric infrared detectors is presented.

Aggarwal, M. D↗

Pyroelectric Materials for Uncooled Infrared Detectors: Processing, Properties, and Applications

Uncooled pyroelectric detectors find applications in diverse and wide areas such as industrial production; automotive; aerospace applications for satellite-borne ozone sensors assembled with an infrared spectrometer; health care; space exploration; imaging systems for ships, cars, and aircraft; and military and security surveillance systems. These detectors are the prime candidates for NASA s thermal infrared detector requirements. In this Technical Memorandum, the physical phenomena underlying the operation and advantages of pyroelectric infrared detectors is introduced. A list and applications of important ferroelectrics is given, which is a subclass of pyroelectrics. The basic concepts of processing of important pyroelectrics in various forms are described: single crystal growth, ceramic processing, polymer-composites preparation, and thin- and thick-film fabrications. The present status of materials and their characteristics and detectors figures-of-merit are presented in detail. In the end, the unique techniques demonstrated for improving/enhancing the performance of pyroelectric detectors are illustrated. Emphasis is placed on recent advances and emerging technologies such as thin-film array devices and novel single crystal sensors.

Aggarwal, M. D.↗

Insight into Pyroelectricity and Phase Transitions in Ferroelectrics from Nonequilibrium Approach: The Case of PbTiO 3

Computational methodology is proposed to simulate time dependent temperature variations via thermostat approach. Here, the methodology is applied to study pyroelectricity under nonequilibrium conditions in prototypical ferroelectric PbTiO 3 . It is found that at room temperature the nonequilibrium effects in pyroelectricity begin manifesting above 1.0 THz and originate from the overlap with the intrinsic soft mode frequency. Therefore, the proposed computational methodology can be used to predict equilibrium pyroelectric response by choosing a frequency of temperature variation below the intrinsic polar mode frequencies for the material. Probing the dynamics of ferroelectric phase transition with the proposed methodology revealed that it takes about a nanosecond for the computational supercell to undergo phase transition. It is concluded that computational techniques capable of simulating picoseconds can be used to compute pyroelectric response from nonequilibrium dynamical approach while those that can reach nanoseconds are suitable for simulating phase transitions in ferroelectrics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗