More Like this

1. Structural phase purification of bulk HfO 2 :Y through pressure cycling

   https://doi.org/10.1073/pnas.2312571121  

   Musfeldt, J. L. ; Singh, Sobhit ; Fan, Shiyu ; Gu, Yanhong ; Xu, Xianghan ; Cheong, S.-W. ; Liu, Z. ; Vanderbilt, David ; Rabe, Karin M. ( January 2024 , Proceedings of the National Academy of Sciences)

   We combine synchrotron-based infrared absorption and Raman scattering spectroscopies with diamond anvil cell techniques and first-principles calculations to explore the properties of hafnia under compression. We find that pressure drives HfO${}_2$:7%Y from the mixed monoclinic ($P{2}_1/c$)$+$antipolar orthorhombic ($\mathit{Pbca}$) phase to pure antipolar orthorhombic ($\mathit{Pbca}$) phase at approximately 6.3 GPa. This transformation is irreversible, meaning that upon release, the material is kinetically trapped in the$\mathit{Pbca}$metastable state at 300 K. Compression also drives polar orthorhombic ($Pca{2}_1$) hafnia into the tetragonal ($P{4}_2/nmc$) phase, although the latter is not metastable upon release. These results are unified by an analysis of the energy landscape. The fact that pressure allows us to stabilize targeted metastable structures with less Y stabilizer is important to preserving the flat phonon band physics of pure HfO${}_2$.

    

   more » « less
2. Zintl Phase Compounds Mg3Sb2−xBix (x = 0, 1, and 2) Monolayers: Electronic, Phonon and Thermoelectric Properties From ab Initio Calculations

   https://doi.org/10.3389/fmech.2022.876655  

   Chang, Zheng ; Ma, Jing ; Yuan, Kunpeng ; Zheng, Jiongzhi ; Wei, Bin ; Al-Fahdi, Mohammed ; Gao, Yufei ; Zhang, Xiaoliang ; Shao, Hezhu ; Hu, Ming ; et al ( April 2022 , Frontiers in Mechanical Engineering)

   The Mg 3 Sb 2− x Bi x family has emerged as the potential candidates for thermoelectric applications due to their ultra-low lattice thermal conductivity ( κ L ) at room temperature (RT) and structural complexity. Here, using ab initio calculations of the electron-phonon averaged (EPA) approximation coupled with Boltzmann transport equation (BTE), we have studied electronic, phonon and thermoelectric properties of Mg 3 Sb 2− x Bi x (x = 0, 1, and 2) monolayers. In violation of common mass-trend expectations, increasing Bi element content with heavier Zintl phase compounds yields an abnormal change in κ L in two-dimensional Mg 3 Sb 2− x Bi x crystals at RT (∼0.51, 1.86, and 0.25 W/mK for Mg 3 Sb 2 , Mg 3 SbBi, and Mg 3 Bi 2 ). The κ L trend was detailedly analyzed via the phonon heat capacity, group velocity and lifetime parameters. Based on quantitative electronic band structures, the electronic bonding through the crystal orbital Hamilton population (COHP) and electron local function analysis we reveal the underlying mechanism for the semiconductor-semimetallic transition of Mg 3 Sb 2-− x Bi x compounds, and these electronic transport properties (Seebeck coefficient, electrical conductivity, and electronic thermal conductivity) were calculated. We demonstrate that the highest dimensionless figure of merit ZT of Mg 3 Sb 2− x Bi x compounds with increasing Bi content can reach ∼1.6, 0.2, and 0.6 at 700 K, respectively. Our results can indicate that replacing heavier anion element in Zintl phase Mg 3 Sb 2− x Bi x materials go beyond common expectations (a heavier atom always lead to a lower κ L from Slack’s theory), which provide a novel insight for regulating thermoelectric performance without restricting conventional heavy atomic mass approach. 

   more » « less
3. Enhanced Piezoelectric, Ferroelectric, and Electrostrictive Properties of Lead‐Free (1‐ x )BCZT‐( x )BCST Electroceramics with Energy Harvesting Capability

   https://doi.org/10.1002/smll.202300549  

   Baraskar, Bharat G. ; Kolekar, Yesappa D. ; Thombare, Balu. R. ; James, Ajit. R. ; Kambale, Rahul C. ; Ramana, C. V. ( May 2023 , Small)

   Next‐generation electronics and energy technologies can now be developed as a result of the design, discovery, and development of novel, environmental friendly lead (Pb)‐free ferroelectric materials with improved characteristics and performance. However, there have only been a few reports of such complex materials’ design with multi‐phase interfacial chemistry, which can facilitate enhanced properties and performance. In this context, herein, novel lead‐free piezoelectric materials (1‐x)Ba_0.95Ca_0.05Ti_0.95Zr_0.05O₃‐(x)Ba_0.95Ca_0.05Ti_0.95Sn_0.05O₃, are reported, which are represented as (1‐x)BCZT‐(x)BCST, with demonstrated excellent properties and energy harvesting performance. The (1‐x)BCZT‐(x)BCST materials are synthesized by high‐temperature solid‐state ceramic reaction method by varyingxin the full range (x= 0.00–1.00). In‐depth exploration research is performed on the structural, dielectric, ferroelectric, and electro‐mechanical properties of (1‐x)BCZT‐(x)BCST ceramics. The formation of perovskite structure for all ceramics without the presence of any impurity phases is confirmed by X‐ray diffraction (XRD) analyses, which also reveals that the Ca²⁺, Zr⁴⁺, and Sn⁴⁺are well dispersed within the BaTiO₃lattice. For all (1‐x)BCZT‐(x)BCST ceramics, thorough investigation of phase formation and phase‐stability using XRD, Rietveld refinement, Raman spectroscopy, high‐resolution transmission electron microscopy (HRTEM), and temperature‐dependent dielectric measurements provide conclusive evidence for the coexistence of orthorhombic + tetragonal (Amm2+P4mm) phases at room temperature. The steady transition ofAmm2crystal symmetry toP4mmcrystal symmetry with increasingxcontent is also demonstrated by Rietveld refinement data and related analyses. The phase transition temperatures, rhombohedral‐orthorhombic (T_R‐O), orthorhombic‐ tetragonal (T_O‐T), and tetragonal‐cubic (T_C), gradually shift toward lower temperature with increasingxcontent. For (1‐x)BCZT‐(x)BCST ceramics, significantly improved dielectric and ferroelectric properties are observed, including relatively high dielectric constantε_r≈ 1900–3300 (near room temperature),ε_r≈ 8800–12 900 (near Curie temperature), dielectric loss, tanδ≈ 0.01–0.02, remanent polarizationP_r≈ 9.4–14 µC cm⁻², coercive electric fieldE_c≈ 2.5–3.6 kV cm⁻¹. Further, high electric field‐induced strainS≈ 0.12–0.175%, piezoelectric charge coefficientd₃₃≈ 296–360 pC N⁻¹, converse piezoelectric coefficient ≈ 240–340 pm V⁻¹, planar electromechanical coupling coefficientk_p≈ 0.34–0.45, and electrostrictive coefficient (Q₃₃)_avg≈ 0.026–0.038 m⁴C⁻²are attained. Output performance with respect to mechanical energy demonstrates that the (0.6)BCZT‐(0.4)BCST composition (x= 0.4) displays better efficiency for generating electrical energy and, thus, the synthesized lead‐free piezoelectric (1‐x)BCZT‐(x)BCST samples are suitable for energy harvesting applications. The results and analyses point to the outcome that the (1‐x)BCZT‐(x)BCST ceramics as a potentially strong contender within the family of Pb‐free piezoelectric materials for future electronics and energy harvesting device technologies.

    

   more » « less
4. The intrinsic thermal transport properties of the biphenylene network and the influence of hydrogenation: a first-principles study

   https://doi.org/10.1039/D1TC04154A  

   Zhang, Pei ; Ouyang, Tao ; Tang, Chao ; He, Chaoyu ; Li, Jin ; Zhang, Chunxiao ; Hu, Ming ; Zhong, Jianxin ( December 2021 , Journal of Materials Chemistry C)

   Utilizing first-principles calculations combined with phonon Boltzmann transport theory up to fourth-order anharmonicity, we systematically investigate the thermal transport properties of the biphenylene network [BPN, recently synthesized experimentally by Fan et al. , Science , 2021, 372 , 852–856] and hydrogenated BPN (HBPN). The calculations show that four-phonon scattering significantly affects the lattice thermal conductivity ( κ ) of BPN. At room temperature, the κ of BPN is reduced from 582.32 (1257.07) W m −1 K −1 to 309.56 (539.88) W m −1 K −1 along the x ( y ) direction after considering the four-phonon scattering. Moreover, our results demonstrate that the thermal transport in BPN could also be greatly suppressed by hydrogenation, where the κ of HBPN along the x ( y ) direction is merely 16.62% (10.14%) of that of pristine BPN at 300 K. The mechanism causing such an obvious decrease of κ of HBPN is identified to be due to the enhanced phonon scattering rate and reduced group velocity, which is further revealed by the increased scattering phase space and weakened C–C bond. The results presented in this work shed light on the intrinsic thermal transport features of BPN and HBPN, which will help us to understand the phonon transport processes and pave the way for their future developments in the thermal field. 

   more » « less
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.

    

   more » « less