Phase transitions and electrocaloric effects of (111)-oriented K0.5Na0.5NbO3 epitaxial films: effect of external stress and misfit strains

Bai Gang; Han Yu-Hang; Gao Cun-Fa

doi:10.7498/aps.71.20220234

Abstract

Lead-free K_1–xNa_xNbO₃ thin films, as a candidate for sensors and electromechanical and electrocaloric cooling devices, have increasingly received attention. However, for (111)-oriented films, the relation between phase transitions and electrocaloric effect is not clear. Here, we derive the thermodynamic potential of (111)-oriented thin film ferroelectrics K_1–xNa_xNbO₃ based on the 8^th order polynomial function, and then establish the temperature-misfit strain and out-of-plane stress-in-plane misfit strain phase diagrams and calculate electrocaloric (EC) entropy changes ΔS and temperature changes ΔT. This study focuses on mechanical and orientation controls of room-temperature EC effect of K_0.5Na_0.5NbO₃ films, which is critical for environmentally friendly electrocaloric refrigeration applications in practice. Under the stress-free and zero misfit strain conditions, the (111)-oriented K_0.5Na_0.5NbO₃ film in an electric field of 30 MV/m has a maximum EC ΔT of ～18 K near the rhombohedral ferroelectric-paraelectric phase transition temperature (about 673 K). However, an out-of-plane stress of about –6.7GPa can reduce the optimal operating temperature to room temperature where the K_0.5Na_0.5NbO₃ film has the EC ΔT of ～7.5 K under the action of applied electric field of 30 MV/m. The present work provides theoretical guidance for exploring the strain engineering and orientation engineering of K_1–xNa_xNbO₃-based thin films with optimized electrocaloric and electromechanical properties.

Keywords:

Authors and contacts

1.
College of Integrated Circuit Science and Engineering, Nanjing University of Posts and Telecommunications, Nanjing 210026, China
2.
State Key Laboratory of Mechanics and Control of Mechanical Structures, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, China

Corresponding author: Bai Gang, baigang@njupt.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 51602159).

[1]	Moya X, Kar-Narayan S, Mathur N 2014 Nat. Mater. 13 439 Google Scholar
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图 1 (111)取向K_0.5Na_0.5NbO₃薄膜的热力学计算结果　(a) 温度-失配应变相图和(b) 没有外加电场的薄膜极化分布; 薄膜在20 MV/m 的电场下的(c)极化分布、(d)极化变化分布、(e)电卡熵变化ΔS和(f)电卡温度变化ΔT. 粗线和细线分别表示一阶和二阶相变

Figure 1. Thermodynamic calculated results for (111)-oriented K_0.5Na_0.5NbO₃ films: (a) The temperature-misfit strain phase diagram and (b) the distribution of polarization without electric field; (c) the distribution of polarization, (d) the distribution of polarization change, (e) the electrocaloric (EC) entropy change ΔS, and (f) the EC temperature change ΔT with temperature and misfit strain for (111)-oriented K_0.5Na_0.5NbO₃ films under the electric field of 20 MV/m. Thick and thin lines denote the first-order and second-order phase transitions, respectively.

DownLoad: Full-Size Img PowerPoint

图 2 (a)—(c)在ΔE = 20 MV/m, 不同应变下, (111)取向K_0.5Na_0.5NbO₃薄膜的极化变化、电卡 ΔS和电卡ΔT随温度的变化; (d)—(f)在u_m= 0, 不同电场下, (111)取向K_0.5Na_0.5NbO₃薄膜的极化变化、电卡ΔS和电卡ΔT随温度的变化

Figure 2. Polarization changes, the EC entropy change ΔS and the EC temperature change ΔT change with temperature for (111)-oriented K_0.5Na_0.5NbO₃ films: (a)–(c) Under different strains at ΔE = 20 MV/m; (d)–(f) under different electric fields and strain-free conditions.

DownLoad: Full-Size Img PowerPoint

图 3 室温下(111)取向K_0.5Na_0.5NbO₃薄膜的热力学计算结果　(a) 面外应力-面内错配应变相图和(b)没有电场的极化分布; 电场20 MV/m下, (c)极化、(d)极化变化、(e)电卡ΔS和(f)电卡ΔT在相图中的分布

Figure 3. Thermodynamic calculated results for (111)-oriented K_0.5Na_0.5NbO₃ films: (a) Out-of-plane stress- misfit strain phase diagram and (b) the distribution of polarization without electric field; (c) the distribution of polarization, (d) polarization change, (e) the EC entropy change ΔS, and (f) the EC temperature change ΔT with external stress and misfit strain under the electric field of 20 MV/m at room temperature (298 K). Thick and thin lines denote the first-order and second-order phase transitions, respectively.

DownLoad: Full-Size Img PowerPoint

图 4 (a)—(c)在ΔE = 20 MV/m, 不同错配应变下(111)取向K_0.5Na_0.5NbO₃薄膜的极化变化、电卡ΔS和电卡ΔT随面外应力的变化; (d)—(f)在u_m= –0.02, 不同电场下, (111)取向K_0.5Na_0.5NbO₃薄膜的极化变化、电卡 ΔS和电卡ΔT随面外应力的变化

Figure 4. Polarization changes, the EC entropy change ΔS and the EC temperature change ΔT change with out-of-plane stress for (111)-oriented K_0.5Na_0.5NbO₃ films: (a)–(c) Under different misfit strains at ΔE = 20 MV/m; (d)–(f) under different electric fields and the misfit strain of –0.02.

DownLoad: Full-Size Img PowerPoint

[1]	Moya X, Kar-Narayan S, Mathur N 2014 Nat. Mater. 13 439 Google Scholar
[2]	Mischenko A, Zhang Q, Scott J, Whatmore R, Mathur N 2006 Science 311 1270 Google Scholar
[3]	Shi J, Han D, Li Z, et al. 2019 Joule 3 1200 Google Scholar
[4]	Meng Y, Pu J, Pei Q 2021 Joule 5 780 Google Scholar
[5]	Torello A, P. Lheritier P, Usui T, et al. 2020 Science 370 125 Google Scholar
[6]	Wang Y, Zhang Z, Usui T, et al. 2020 Science 370 129 Google Scholar
[7]	Nair B, Usui T, Crossley S, et al. 2019 Nature 33 468
[8]	Yasuyoshi S, Hisaaki T, Toshihiko T, Tatsuhiko N, Kazumasa T, Takahiko H, Toshiatsu N, Masaya N 2004 Nature 432 84 Google Scholar
[9]	Shrout T, Zhang S 2007 J. Electroceram. 19 185 Google Scholar
[10]	Zhang M, Wang K, Du Y, Dai G, Sun W, Li G, Hu D, Thong H, Zhao C, Xi X, Yue Z, Li J 2017 J. Am. Chem. Soc. 139 3889 Google Scholar
[11]	Li J, Wang K, Zhu F, Cheng L, Yao F 2013 J. Am. Ceram. Soc. 96 3677 Google Scholar
[12]	Gupta A, Kumar R, Singh S 2018 Scr. Mater. 143 5 Google Scholar
[13]	Wang X, Wu J, Dkhil B, Xu B, Wang X, Dong G, Yang G, Lou X 2017 Appl. Phys. Lett. 110 063904 Google Scholar
[14]	Zhao X, Wang J, Chen L 2020 Appl. Phys. Lett. 116 092902 Google Scholar
[15]	Pertsev N, Zembilgotov A, Tagantsev A 1998 Phys. Rev. Lett. 80 1988 Google Scholar
[16]	Bai G, Ma W 2010 Physica B 405 190 Google Scholar
[17]	刘迪, 王静, 王俊升, 黄厚兵 2020 物理学报 69 127801 Google Scholar Liu D, Wang J, Wang J S, Huang H B 2020 Acta Phys. Sin. 69 127801 Google Scholar
[18]	高荣贞, 王静, 王俊升, 黄厚兵 2020 物理学报 69 217801 Google Scholar Gao R, Wang J, Wang J, Huang H 2020 Acta Phys. Sin. 69 217801 Google Scholar
[19]	Zhou M, Wang J, Chen L, Nan C 2018 J. Appl. Phys. 123 154106 Google Scholar
[20]	Bai G, Qin K, Xie Q, Yan X, Gao C, Liu Z 2017 Mater. Lett. 186 146 Google Scholar
[21]	Pohlmann H, Wang J, Wang B, Chen L 2017 Appl. Phys. Lett. 110 102906 Google Scholar
[22]	Wang J, Fortino D, Wang B, Zhao X, Chen L 2020 Adv. Mater. 32 1906224 Google Scholar
[23]	Gao R, Shi X, Wang J, Zhang G, Huang H 2021 Adv. Funct. Mater. 31 2104393 Google Scholar
[24]	Bai G, Xie Q, Liu Z, Wu D 2015 J. Appl. Phys. 118 074101 Google Scholar
[25]	Shan D, Lei C, Cai Y, et al. 2021 Int. J. Solids Struct. 216 59 Google Scholar
[26]	Harrington S, Zhai J, Denev S, et al. 2011 Nat. Nanotechnol. 6 491 Google Scholar
[27]	Emelyanov A, Pertsev N, Kholkin A 2002 Phys. Rev. B 66 214108 Google Scholar
[28]	Sun X, Huang H, Wang J, Wen Y, Dang Z 2019 J. Alloys. Compd. 777 821 Google Scholar
[29]	Liu D, Bai G, Gao C 2020 J. Appl. Phys. 127 154101 Google Scholar
[30]	白刚, 林翠, 刘端生, 许杰, 李卫, 高存法 2021 物理学报 70 127701 Google Scholar Bai G, Lin C, Liu D S, Xu J, Li W, Gao C F 2021 Acta Phys. Sin. 70 127701 Google Scholar
[31]	Peng B, Zhang Q, Gang B, et al. 2019 Energy Environ. Sci. 12 1708 Google Scholar
[32]	Tagantsev A, Pertsev N, Muralt P, Setter N 2001 Phys. Rev. B 65 012104 Google Scholar
[33]	Akcay G, Misirlioglu I B, Alpay S P 2006 Appl. Phys. Lett. 89 042903 Google Scholar
[34]	Zhang J X, Li Y L, Wang Y, Liu Z K, Chen L Q 2007 J. Appl. Lett. 101 114105
[35]	Wu H, Ma X, Zhang Z, Zeng J, Wang J, Chai G 2016 AIP Adv. 6 015309 Google Scholar
[36]	Li C, Huang Y, Wang J, et al. 2021 Npj Comput. Mater. 7 1 Google Scholar
[37]	Valant M 2012 Prog. Mater. Sci. 57 980 Google Scholar
[38]	Liu Y, Scott J, Dkhil B 2016 Appl. Phys. Rev. 3 031102 Google Scholar

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Phase transitions and electrocaloric effects of (111)-oriented K_0.5Na_0.5NbO₃ epitaxial films: effect of external stress and misfit strains

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Corresponding author: Bai Gang, baigang@njupt.edu.cn

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