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1. Exploring the Pb _{1− x} Sr _x HfO ₃ System and Potential for High Capacitive Energy Storage Density and Efficiency

   https://doi.org/10.1002/adma.202105967  

   Acharya, Megha; Banyas, Ella; Ramesh, Maya; Jiang, Yizhe; Fernandez, Abel; Dasgupta, Arvind; Ling, Handong; Hanrahan, Brendan; Persson, Kristin; Neaton, Jeffrey_B; et al (October 2021, Advanced Materials)

   Abstract The hafnate perovskites PbHfO₃(antiferroelectric) and SrHfO₃(“potential” ferroelectric) are studied as epitaxial thin films on SrTiO₃(001) substrates with the added opportunity of observing a morphotropic phase boundary (MPB) in the Pb_1−xSr_xHfO₃system. The resulting (240)‐oriented PbHfO₃(Pba2) films exhibited antiferroelectric switching with a saturation polarization ≈53 µC cm⁻²at 1.6 MV cm⁻¹, weak‐field dielectric constant ≈186 at 298 K, and an antiferroelectric‐to‐paraelectric phase transition at ≈518 K. (002)‐oriented SrHfO₃films exhibited neither ferroelectric behavior nor evidence of a polarP4mmphase . Instead, the SrHfO₃films exhibited a weak‐field dielectric constant ≈25 at 298 K and no signs of a structural transition to a polar phase as a function of temperature (77–623 K) and electric field (–3 to 3 MV cm⁻¹). While the lack of ferroelectric order in SrHfO₃removes the potential for MPB, structural and property evolution of the Pb_1−xSr_xHfO₃(0 ≤x < 1) system is explored. Strontium alloying increased the electric‐breakdown strength (E_B) and decreased hysteresis loss, thus enhancing the capacitive energy storage density (U_r) and efficiency (η). The composition, Pb_0.5Sr_0.5HfO₃produced the best combination ofE_B = 5.12 ± 0.5 MV cm⁻¹,U_r = 77 ± 5 J cm⁻³, and η = 97 ± 2%, well out‐performing PbHfO₃and other antiferroelectric oxides. 

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2. Strengthened relaxor behavior in (1− x )Pb(Fe _0.5 Nb _0.5 )O ₃ – x BiFeO ₃

   https://doi.org/10.1039/C9TC05883D  

   Prah, Uroš; Dragomir, Mirela; Rojac, Tadej; Benčan, Andreja; Broughton, Rachel; Chung, Ching-Chang; Jones, Jacob L.; Sherbondy, Rachel; Brennecka, Geoff; Uršič, Hana (March 2020, Journal of Materials Chemistry C)

   null (Ed.)

   A systematic study of (1− x )Pb(Fe 0.5 Nb 0.5 )O 3 – x BiFeO 3 ( x = 0–0.5) was performed by combining dielectric and electromechanical measurements with structural and microstructural characterization in order to investigate the strengthening of the relaxor properties when adding BiFeO 3 into Pb(Fe 0.5 Nb 0.5 )O 3 and forming a solid solution. Pb(Fe 0.5 Nb 0.5 )O 3 crystalizes in monoclinic symmetry exhibiting ferroelectric-like polarization versus electric field ( P–E ) hysteresis loop and sub-micron-sized ferroelectric domains. Adding BiFeO 3 to Pb(Fe 0.5 Nb 0.5 )O 3 favors a pseudocubic phase and a gradual strengthening of the relaxor behavior of the prepared ceramics. This is indicated by a broadening of the peak in temperature-dependent permittivity, narrowing of P–E hysteresis loops and decreasing size of ferroelectric domains resulting in polar nanodomains for x = 0.20 composition. The relaxor behavior was additionally confirmed by Vogel–Fulcher analysis. For the x ≥ 0.30 compositions, broad high-temperature anomalies are observed in dielectric permittivity versus temperature measurements in addition to the frequency-dispersive peak located close to room temperature. These samples also exhibit pinched P–E hysteresis loops. The observed pinching is most probably related to the reorganization of polar nanoregions under the electric field as shown by synchrotron X-ray diffraction measurements as well as by piezo-response force microscopy analysis, while in part affected by the presence of charged point defects and anti-ferroelectric order, as indicated from rapid cooling experiments and high-resolution transmission electron microscopy, respectively. 

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3. Epitaxial SrTiO ₃ films with dielectric constants exceeding 25,000

   https://doi.org/10.1073/pnas.2202189119  

   Yang, Zhifei; Lee, Dooyong; Yue, Jin; Gabel, Judith; Lee, Tien-Lin; James, Richard D.; Chambers, Scott A.; Jalan, Bharat (June 2022, Proceedings of the National Academy of Sciences)

   SrTiO 3 (STO) is an incipient ferroelectric perovskite oxide for which the onset of ferroelectric order is suppressed by quantum fluctuations. This property results in a very large increase in static dielectric constant from ∼300 at room temperature to ∼20,000 at liquid He temperature in bulk single crystals. However, the low-temperature dielectric constant of epitaxial STO films is typically a few hundred to a few thousand. Here, we use all-epitaxial capacitors of the form n -STO/undoped STO/ n -STO (001) prepared by hybrid molecular beam epitaxy, to demonstrate intrinsic dielectric constants of an unstrained STO (001) film exceeding 25,000. We show that the n -STO/undoped STO interface plays a critically important role not previously considered in determining the dielectric properties that must be properly accounted for to determine the intrinsic dielectric constant. 

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4. Structural anisotropy in Sb thin films

   https://doi.org/10.1063/5.0159670  

   Adhikari, Pradip; Wijesinghe, Anuradha; Rathore, Anjali; Yoo, Timothy Jinsoo; Kim, Gyehyeon; Yeom, Sinchul; Lee, Hyoung-Taek; Mazza, Alessandro R; Sohn, Changhee; Park, Hyeong-Ryeol; et al (January 2024, APL Materials)

   Sb thin films have attracted wide interest due to their tunable band structure, topological phases, high electron mobility, and thermoelectric properties. We successfully grow epitaxial Sb thin films on a closely lattice-matched GaSb(001) surface by molecular beam epitaxy. We find a novel anisotropic directional dependence on their structural, morphological, and electronic properties. The origin of the anisotropic features is elucidated using first-principles density functional theory (DFT) calculations. The growth regime of crystalline and amorphous Sb thin films was determined by mapping the surface reconstruction phase diagram of the GaSb(001) surface under Sb2 flux, with confirmation of structural characterizations. Crystalline Sb thin films show a rhombohedral crystal structure along the rhombohedral (211) surface orientation parallel to the cubic (001) surface orientation of the GaSb substrate. At this coherent interface, Sb atoms are aligned with the GaSb lattice along the [1̄10] crystallographic direction but are not aligned well along the [110] crystallographic direction, which results in anisotropic features in reflection of high-energy electron diffraction patterns, misfit dislocation formation, surface morphology, and transport properties. Our DFT calculations show that the preferential orientation of the rhombohedral Sb (211) plane may originate from the GaSb surface, where Sb atoms align with the Ga and Sb atoms on the reconstructed surface. The formation energy calculations confirm the stability of the experimentally observed structures. Our results provide optimal film growth conditions for further studies of novel properties of Bi1−xSbx thin films with similar lattice parameters and an identical crystal structure, as well as functional heterostructures of them with III–V semiconductor layers along the (001) surface orientation, supported by a theoretical understanding of the anisotropic film orientation. 

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5. Resolving Mechanical Properties and Morphology Evolution of Free‐Standing Ferroelectric Hf _0.5 Zr _0.5 O ₂

   https://doi.org/10.1002/adem.202101221  

   Tharpe, Troy; Zheng, Xu-Qian; Feng, Philip_X-L; Tabrizian, Roozbeh (October 2021, Advanced Engineering Materials)

   Advances in creating polar structures in atomic‐layered hafnia‐zirconia (Hf_xZr_1−xO₂) films not only augurs extensive growth in studying ferroelectric nanoelectronics and neuromorphic devices, but also spurs opportunities for exploring novel integrated nanoelectromechanical systems (NEMS). Design and implementation of Hf_xZr_1−xO₂NEMS transducers necessitates accurate knowledge of elastic and electromechanical properties. Up to now, all experimental approaches for extraction of morphological content, elastic, and electromechanical properties of Hf_xZr_1−xO₂are based on solidly mounted structures, highly stressed films, and electroded architectures. Unlike Hf_xZr_1−xO₂layers embedded in electronics, NEMS transducers require free‐standing structures with highly contrasted mechanical boundaries and stress profiles. Here, a nanoresonator‐based approach for simultaneous extraction of Young's modulus and residual stress in free‐standing ferroelectric Hf_0.5Zr_0.5O₂films is presented. High quality factor resonance modes of nanomechanical resonators created in predominantly orthorhombic Hf_0.5Zr_0.5O₂films are measured using nondestructive optical transduction. Further, the evolution of morphology during creation of free‐standing Hf_0.5Zr_0.5O₂structures is closely mapped using X‐ray diffraction measurements, clearly showing transformation of ferroelectric orthorhombic to nonpolar monoclinic phase upon stress relaxation. The extracted Young's modulus of 320.0 ± 29.4 GPa and residual stress ofσ = 577.4 ± 24.1 MPa show the closest match with theoretical calculations for orthorhombic Hf_0.5Zr_0.5O₂. 

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