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Pyroelectric thin films—Past, present, and future

Pyroelectrics are a material class that undergoes a change in polarization as the temperature of the system is varied. This effect can be utilized for applications ranging from thermal imaging and sensing to waste-heat energy conversion to thermally driven electron emission. Here, we review recent advances in the study and utilization of thin-film pyroelectrics. Leveraging advances in modeling, synthesis, and characterization has provided a pathway forward in one of the more poorly developed subfields of ferroelectricity. We introduce the complex physical phenomena of pyroelectricity, briefly explore the history of work in this space, and highlight not only new advances in the direct measurement of such effects but also how our ability to control thin-film materials is changing our understanding of this response. Finally, we discuss recent advances in thin-film pyroelectric devices and introduce a number of potentially new directions the field may follow in the coming years.

36 MATERIALS SCIENCE↗

The strain-induced transitions of the piezoelectric, pyroelectric, and electrocaloric properties of the CuInP 2 S 6 films

Low-dimensional ferroelectrics, ferrielectrics, and antiferroelectrics are of urgent scientific interest due to their unusual polar, piezoelectric, electrocaloric, and pyroelectric properties. The strain engineering and strain control of the ferroelectric properties of layered two-dimensional van der Waals materials, such as CuInP 2 (S,Se) 6 monolayers, thin films, and nanoflakes, are of fundamental interest and especially promising for their advanced applications in nanoscale nonvolatile memories, energy conversion and storage, nano-coolers, and sensors. Here, we study the polar, piezoelectric, electrocaloric, and pyroelectric properties of thin strained films of a ferrielectric CuInP 2 S 6 covered by semiconducting electrodes and reveal an unusually strong effect of a mismatch strain on these properties. In particular, the sign of the mismatch strain and its magnitude determine the complicated behavior of piezoelectric, electrocaloric, and pyroelectric responses. The strain effect on these properties is opposite, i.e., “anomalous,” in comparison with many other ferroelectric films, for which the out-of-plane remanent polarization, piezoelectric, electrocaloric, and pyroelectric responses increase strongly for tensile strains and decrease or vanish for compressive strains.

antiferroelectricity↗

The pyroelectric properties of TGS for application in infrared detection

The pyroelectric property of triglycine sulfate and its application in the detection of infrared radiation are described. The detectivities of pyroelectric detectors and other types of infrared detectors are compared. The thermal response of a pyroelectric detector element and the resulting electrical response are derived in terms of the material parameters. The noise sources which limit the sensitivity of pyroelectric detectors are described, and the noise equivalent power for each noise source is given as a function of frequency and detector area.

Kroes, R. L.↗

Pyroelectric detector arrays

A pyroelectric detector array and the method for using it are described. A series of holes formed through a silicon dioxide layer on the surface of a silicon substrate forms the mounting fixture for the pyroelectric detector array. A series of nontouching strips of indium are formed around the holes to make contact with the backside electrodes and form the output terminals for individual detectors. A pyroelectric detector strip with front and back electrodes, respectively, is mounted over the strips. Biasing resistors are formed on the surface of the silicon dioxide layer and connected to the strips. A metallized pad formed on the surface of layer is connected to each of the biasing resistors and to the film to provide the ground for the pyroelectric detector array.

Fripp, A. L.↗

Effect of space exposure on pyroelectric infrared detectors

Pyroelectric detectors are one of the many different types of infrared radiation detectors. 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 of the experiment was to determine the effects of launch and space exposure on the performance of commercially available pyroelectric detectors. The approach was to measure performance parameters of the detectors before and after flight on the Long-Duration Exposure Facility (LDEF) and determine the loss of detector performance. The experiment was passive; no data was taken during flight.

Robertson, James B.↗

Pyroelectric Sandwich Thermal Energy Harvesters

Systems, methods, and devices of the various embodiments provide pyroelectric sandwich thermal energy harvesters. In the various embodiment pyroelectric sandwich thermal energy harvesters, generated electrical energy may be stored in a super-capacitor/battery as soon as it is generated. The various embodiment pyroelectric sandwich thermal energy harvesters may harvest electrical energy from any environment where temperature variations occur. The various embodiment pyroelectric sandwich thermal energy harvesters may be power sources for space equipment and vehicles in space and/or on earth, as well as the for wireless sensor networks, such as health monitoring systems of oil pipes, aircraft, bridges, and buildings.

Xu, Tian-Bing↗

Neutron generation using pyroelectric crystals

According to one embodiment, a method for producing a directed neutron beam 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 to produce a neutron beam, and directing the ion beam onto the deuterated or tritiated target to make neutrons using at least one of a voltage of the pyroelectric crystal, and a high gradient insulator (HGI) surrounding the pyroelectric crystal. The directionality of the neutron beam is controlled by changing the accelerating voltage of the system. Other methods are presented as well.

Tang, Vincent↗

Efficient Broadband Terahertz Generation by Above‐Band‐Gap Excitation of the Pyroelectric ZnSnN 2

Terahertz (THz) radiation is a powerful probe of low-energy excitations in all phases of matter. However, it remains a challenge to find materials that efficiently generate THz radiation in a broad range of frequencies following optical excitation. Here, we investigate a pyroelectric material, ZnSnN 2 , and find that its above-band-gap excitation results in the efficient formation of an ultrafast photocurrent generating THz radiation. The resulting THz electric field spans a frequency range from below 1 THz to above 30 THz. The results suggest that the photocurrent is primarily driven by an ultrafast pyroelectric effect where the photo-excited carriers screen the spontaneous electric polarization of ZnSnN 2 . Strong structural disorder reduces the photocarrier lifetime significantly and, thus, enables broadband operation. ZnSnN2 shows a similar THz-emitter performance as the best spintronic THz emitters regarding bandwidth and amplitude. The study unveils the large potential of pyroelectric materials as efficient and broadband THz emitters with built-in bias fields.

36 MATERIALS SCIENCE↗

Nanoscale Compositional and Strain Gradients Enable High‐Speed and Amplitude‐Resolved Pyroelectric Sensing

The frequency response of pyroelectric sensors is fundamentally governed by thermal time constant (τth, determined by thermal mass and thermal conductance) and electrical impedance arising from film capacitance and readout circuit. Conventional bulk LiTaO3 detectors are optimized for high responsivity at low modulation frequencies (0.1-10 Hz), possessing a large τth that thermally averages rapid temperature oscillations at elevated modulation frequencies, limiting fidelity in resolving dynamic varying thermal signals. Here, compositional and strain gradients are introduced into 100-nm-thick relaxor-ferroelectric films reducing τth to ≈2 µs and producing built-in potentials (≈1.45 V or 145 kV cm-1) that enhance the pyroelectric coefficient and suppress the dielectric constant. This enables complementary dual-mode operation by enhancing current-mode electrical responsivity and improving the voltage-mode figure of merit - advantageous for superior temperature resolution (ΔTmin ≈ 30 µK). The responsivity peak shifts to near 1 kHz (>2500-times higher than conventional bulk sensors), with measurable responsivity extending to a carrier frequency of 100 kHz and amplitude-resolved detection at modulation frequencies up to 15 kHz. These results establish nanoscale internal-field engineering can reshape electro-thermal trade-off in pyroelectric thin films toward zero-bias, high-thermal-sensitivity, and amplitude-resolved thermal sensing across a wide frequency bandwidth.

Lin, Ching‐Che↗

Influence of the Ozone Dose Time during Atomic Layer Deposition on the Ferroelectric and Pyroelectric Properties of 45 nm-Thick ZrO 2 Films

Over a decade ago, ferroelectricity was discovered in doped HfO 2 thin films. The HfO 2 -based thin films have attracted much attention due to their remarkable scalability and CMOS compatibility. Other than the HfO 2 -based thin films, the undoped ZrO 2 thin films are understudied despite their commonly reported antiferroelectric behavior. However, being of the same fluorite structure as HfO 2 -based thin films, the undoped ZrO 2 also displayed considerable ferroelectricity as demonstrated in recent studies. Here, 45 nm-thick polycrystalline undoped ZrO 2 films are synthesized using atomic layer deposition with different ozone dose times. The ZrO 2 films are crystallized after atomic layer deposition at 350 °C without anneals. In general, the longer ozone dose time causes a lower in-plane tensile stress and oxygen vacancy content, which help facilitate an irreversible non-polar tetragonal to polar orthorhombic phase transition with electric-field cycling. However, the lower in-plane tensile stress and oxygen vacancy content also stabilize the monoclinic phase so that a long ozone dose time (>17.5 s) reduces the ferroelectric behavior. After wake-up cycles, the ZrO 2 thin film with an ozone dose time of 17.5 s exhibits a remanent polarization of 6 μC·cm –2 and a pyroelectric coefficient of -35 μC·K –1 ·m –2 . Moreover, the wake-up behavior is consistent between the ferroelectric and pyroelectric response. As essential factors in optimizing the growth of fluorite-structure thin films for ferroelectric applications, the in-plane tensile stress and oxygen vacancy content significantly influence the ferroelectric and pyroelectric properties. Additionally, the low thermal budget for processing ferroelectric ZrO 2 thin films is valuable for semiconductor back-end-of-line processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Advances in pyroelectric infrared detectors.

Recent improvements in the pyroelectric detector have been due to the development of locked-in polarization, further reduction of the FET leakage current, and reduction of short circuit noise. The pyroelectric detector has been successfully employed in these typical applications: (1) thermograph using a single detector and X-Y scanner, (2) focal plane reticle scanner, (3) linear array thermal imaging system, (4) pyroelectric image tube, (5) radiometers (vertical temperature profile radiometer, carbon dioxide sensor), (6) high speed spectrometer, and (7) laser detector.

Beerman, H. P.↗

Pyroelectric detector arrays

A pryoelectric detector array and the method for making it are described. A series of holes formed through a silicon dioxide layer on the surface of a silicon substrate forms the mounting fixture for the pyroelectric detector array. A series of nontouching strips of indium are formed around the holes to make contact with the backside electrodes and form the output terminals for individual detectors. A pyroelectric detector strip with front and back electrodes, respectively, is mounted over the strip. Biasing resistors are formed on the surface of the silicon dioxide layer and connected to the strips. A metallized pad formed on the surface of the layer is connected to each of the biasing resistors and to the film to provide the ground for the pyroelectric detector array.

Fripp, A. L.↗

Effect of space exposure on pyroelectric infrared detectors (A0135)

The effects of long-duration space exposure and launch environment on the performance of pyroelectric detectors which is important for the prediction of performance degradation, setting exposure limits, or determining shielding requirements was investigated. Air pollution monitoring and thermal mapping of the Earth, which includes the remote sensing of aerosols and limb scanning infrared radiometer projects, requires photodetection in the 6- to 20 micro m region of the spectrum. Pyroelectric detectors can detect radiation in the 1- to 100 micro m region while operating at room temperature. This makes tahe pyroelectric detector a prime candidate to fill the thermal infrared detector requirements.

Robertson, J. B.↗

Pyroelectric materials as electronic pulse detectors of ultraheavy nuclei

The design and testing of ultraheavy-nucleus pulse detectors based on pyroelectric materials are reported, extending the preliminary findings of Tuzzolino (1983) and Simpson and Tuzzolino (1983). Uranium-ion beams of about 240 MeV/u are detected by a 39.5-micron-thick Si detector, degraded to about 175 MeV/u by Al absorbers, and then strike 700-micron-thick polyvinylidene fluoride or 1000-micron-thick LiTaO3 pyroelectric samples. Both detector systems are connected to a coincidence circuit via charge-sensitive preamplifiers, shaping amplifiers with 30-microsec effective time constants, and electronic discriminators. Sample spectra are shown, and the pulse heights measured are found to agree with theoretical calculations to within a factor of about 2. The response of the pyroelectric materials is found to be unaffected by exposure to about 10 Mrad of 2-7-MeV/u heavy ion radiation. With further study and improvement of the detection sensitivity, devices of this type could be applied to large-area space measurements of low ultraheavy-ion fluxes.

Simpson, J. A.↗

Piezoelectric and pyroelectric effects of a crystalline polymer

Polyvinylidene flouride (PVDF) is a crystalline polymer to both piezoelectric and pyroelectric nature. Piezoelectricity produces electrical signals when mechanically deformed, and pyroelectricity is the electrical polarization induced by thermal absorption in crystals. To demonstrate the piezoelectric effect PVDF is subjected to impact loads which produce electrical charges proportional to mechanical stresses. A heat source was used to demonstrate the pyroelectric nature of PVDF. The rise in temperature due to absorbed energy by the polymer produces electrical output. The qualitative test results obtained are graphically reproduced.

Kundu, Nikhil K.↗

Modified triglycine sulphate (TGS) single crystals for pyroelectric infrared detector applications

Effects of caesium and cerium, L-alanine, and caesium plus L-alanine impurities on ferroelectric and pyroelectric properties of TGS crystals are investigated. Dielectric constant and loss, pyroelectric coefficient, spontaneous polarization, and coercive field measurements of these modified crystals, as a function of temperature, are reported. Caesium and cerium did not affect the electrical properties of TGS crystals significantly, whereas L-alanine- and, especially, Cs + L-alanine-doped TGS crystals exhibited promising improvements in pyroelectric properties, up to 48 C, as compared to pure TGS crystals.

Banan, M.↗

Active Pyroelectric Infrared Detector

A noncontact pyroelectric infrared detector is described. A pyroelectric film that also has piezoelectric properties is held in place so that it is free to vibrate. It is electrically stimulated to vibrate at a resonance frequency. The vibrating film forms part of a balanced bridge circuit. As thermal radiation impinges on the film the pyroelectric effect causes the resonance frequency to change, thereby unbalancing the bridge circuit. A differential amplifier tracks the change in voltage across the bridge. The resulting voltage signal is further processed by a bandpass filter and a precision rectifier. The device allows for DC or static temperature measurements without the use of a mechanical chopping device.

Zuckerwar, Allan J.↗

Thermally Stable, Piezoelectric and Pyroelectric Polymeric Substrates and Method Relating Thereto

Production of an electric voltage in response to mechanical excitation (piezoelectricity) or thermal excitation (pyroelectricity) requires a material to have a preferred dipole orientation in its structure. This preferred orientation or polarization occurs naturally in some crystals such as quartz and can be induced into some ceramic and polymeric materials by application of strong electric or mechanical fields. For some materials, a combination of mechanical and electrical orientation is necessary to completely polarize the material. The only commercially available piezoelectric polymer is poly(vinylidene fluoride) (PVF2). However, this polymer has material and process limitations which prohibit its use in numerous device applications where thermal stability is a requirement. By the present invention, thermally stable, piezoelectric and pyroelectric polymeric substrates were prepared from polymers having a softening temperature greater than 1000C. A metal electrode material is deposited onto the polymer substrate and several electrical leads are attached to it. The polymer substrate is heated in a low dielectric medium to enhance molecular mobility of the polymer chains. A voltage is then applied to the polymer substrate inducing polarization. The voltage is then maintained while the polymer substrate is cooled 'freezing in' the molecular orientation. The novelty of the invention resides in the process of preparing the piezoelectric and pyroelectric polymeric substrate. The nonobviousness of the invention is found in heating the polymeric substrate in a low dielectric medium while applying a voltage.

Simpson, Joycelyn O.↗