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1. Magnetron Sputtered Lead Titanates Thin Films for Pyroelectric Applications: Part 1: Epitaxial Growth, Material Characterization

   https://doi.org/10.3390/ma17010221  

   Fathipour, Morteza; Xu, Yanan; Rana, Mukti (January 2024, Materials)

   Pyroelectric materials, are those materials with the property that in the absence of any externally applied electric field, develop a built-in spontaneous polarization in their unit cell structure. They are regarded as ideal detector elements for infrared applications because they can provide fast response time and uniform sensitivity at room temperature over all wavelengths. Crystals of the perovskite Lead Titanate (PbTiO3) family show pyroelectric characteristics and undergo structural phase transitions. They have a high Curie temperature (the temperature at which the material changes from the ferroelectric (polar) to the paraelectric (nonpolar) phase), high pyroelectric coefficient, high spontaneous polarization, low dielectric constant, and constitute important component materials not only useful for infrared detection, but also with vast applications in electronic, optic, and Micro-electromechanical systems (MEMS) devices. However, the preparation of large perfect, and pure single crystals of PbTiO3 is challenging. Additionally, difficulties arise in the application of such bulk crystals in terms of connection to processing circuits, large size, and high voltages required for their operation. A number of thin film fabrication techniques have been proposed to overcome these inadequacies, among which, magnetron sputtering has demonstrated many potentials. By addressing these aspects, the review article aims to contribute to the understanding of the challenges in the field of pyroelectric materials, highlight potential solutions, and showcase the advancements and potentials of pyroelectric perovskite series including PbZrTiO3 (PZT), PbxCa1−x (PZN-PT), etc. for which PbTiO3 is the end member. The review is presented in two parts. Part 1 focuses on material aspects, including preparation methods using magnetron sputtering and material characterization. We take a tutorial approach to discuss the progress made in epitaxial growth of lead titanate-based ceramics prepared by magnetron sputtering and examine how processing conditions may affect the crystalline quality of the growing film by linking to the properties of the substrate/buffer layer, growth substrate temperature, and the oxygen partial pressure in the gas mixture. Careful control and optimization of these parameters are crucial for achieving high-quality thin films with desired structural and morphological characteristics. 

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2. Designing soft pyroelectric and electrocaloric materials using electrets

   https://doi.org/10.1039/C8SM02003E  

   Darbaniyan, Faezeh; Dayal, Kaushik; Liu, Liping; Sharma, Pradeep (January 2019, Soft Matter)

   A temperature variation can electrically polarize a pyroelectric material. In its converse manifestation, the electrocaloric effect entails a change in temperature due to the application of an electric field. These phenomena have wide applications ranging from infrared detection sensors and solid-state refrigeration to energy harvesting. However, the pyroelectric–electrocaloric effect is typically observed in certain classes of hard, brittle crystalline materials that must satisfy a stringent set of lattice symmetry conditions. Some limited experiments have however demonstrated that embedding immobile charges and dipoles in soft foams (thus creating an electret state) may lead to a pyroelectric-like response as well as large deformations desired from soft matter. In this work, we develop a systematic theory for coupled electrical, thermal and mechanical responses of soft electrets. Using simple illustrative examples, we derive closed-form explicit expressions for the pyroelectric and electrocaloric coefficients of electrets. While pyroelectricity in electrets has been noted before, our derived expressions provide a clear quantitative basis to interpret (and eventually design) this effect as well as insights into how the geometrically nonlinear deformation and Maxwell stress give rise to its emergence. We present conditions to obtain a larger pyroelectric and electrocaloric response. In particular, the electrocaloric effect is predicted for the first time in such materials and we show that a proper design and a reasonable choice of materials can lead to a temperature reduction of as much as 1.5 K under the application of electrical fields of 10 MV cm −1 . 

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3. Enhanced pyroelectric properties of Bi1−xLaxFeO3 thin films

   https://doi.org/10.1063/1.5128413  

   Zhang, Lei; Huang, Yen-Lin; Velarde, Gabriel; Ghosh, Anirban; Pandya, Shishir; Garcia, David; Ramesh, Ramamoorthy; Martin, Lane_W (November 2019, APL Materials)

   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 (TC) 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 Bi1−xLaxFeO3 (x = 0–0.45) is probed. While BiFeO3 itself has a high TC, 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 BiFeO3 itself has a rather small pyroelectric coefficient at room temperature (∼−40 µC/m2 K), 15% lanthanum substitution results in an enhancement of the pyroelectric coefficient by 100% which is found to arise from a systematic lowering of TC. 

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4. Ferrielectricity in the Archetypal Antiferroelectric, PbZrO ₃

   https://doi.org/10.1002/adma.202206541  

   Yao, Yulian; Naden, Aaron; Tian, Mengkun; Lisenkov, Sergey; Beller, Zachary; Kumar, Amit; Kacher, Josh; Ponomareva, Inna; Bassiri‐Gharb, Nazanin (December 2022, Advanced Materials)

   Abstract Antiferroelectric materials, where the transition between antipolar and polar phase is controlled by external electric fields, offer exceptional energy storage capacity with high efficiencies, giant electrocaloric effect, and superb electromechanical response. PbZrO₃is the first discovered and the archetypal antiferroelectric material. Nonetheless, substantial challenges in processing phase pure PbZrO₃have limited studies of the undoped composition, hindering understanding of the phase transitions in this material or unraveling the controversial origins of a low‐field ferroelectric phase observed in lead zirconate thin films. Leveraging highly oriented PbZrO₃thin films, a room‐temperature ferrielectric phase is observed in the absence of external electric fields, with modulations of amplitude and direction of the spontaneous polarization and large anisotropy for critical electric fields required for phase transition. The ferrielectric state observations are qualitatively consistent with theoretical predictions, and correlate with very high dielectric tunability, and ultrahigh strains (up to 1.1%). This work suggests a need for re‐evaluation of the fundamental science of antiferroelectricity in this archetypal material. 

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5. Pyroelectric energy conversion with large energy and power density in relaxor ferroelectric thin films

   https://doi.org/10.1038/s41563-018-0059-8  

   Pandya, Shishir; Wilbur, Joshua; Kim, Jieun; Gao, Ran; Dasgupta, Arvind; Dames, Chris; Martin, Lane W. (April 2018, Nature Materials)

   The need for efficient energy utilization is driving research into ways to harvest ubiquitous waste heat. Here, we explore pyroelectric energy conversion from low-grade thermal sources that exploits strong field- and temperature-induced polarization susceptibilities in the relaxor ferroelectric 0.68Pb(Mg1/3Nb2/3)O3–0.32PbTiO3. Electric-field-driven enhancement of the pyroelectric response (as large as − 550 μC m−2 K−1) and suppression of the dielectric response (by 72%) yield substantial figures of merit for pyroelectric energy conversion. Field- and temperature-dependent pyroelectric measurements highlight the role of polarization rotation and field-induced polarization in mediating these effects. Solid-state, thin-film devices that convert lowgrade heat into electrical energy are demonstrated using pyroelectric Ericsson cycles, and optimized to yield maximum energy density, power density and efficiency of 1.06 J cm−3, 526 W cm−3 and 19% of Carnot, respectively; the highest values reported to date and equivalent to the performance of a thermoelectric with an effective ZT ≈ 1.16 for a temperature change of 10 K. Our findings suggest that pyroelectric devices may be competitive with thermoelectric devices for low-grade thermal harvesting. 

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