-
Organic ferroelectrics are desirable for the application in the field of wearable electronics due to their eco-friendly process-ability, mechanical flexibility, low processing temperatures, and lightweight. In this work, we used five organic groups as substitution for organic cation and studied the effects of organic cations on the structural stability, electronic structure, mechanical properties and spontaneous polarization of metal-free perovskite A-NH4-(PF6)3(A=MDABCO, CNDABCO, ODABCO, NODABCO, SHDABCO) through first-principles calculations. Firstly, the stability of the five materials was calculated by molecular dynamics simulations, and the energy of all systems is negative and stable after 500 fs, which demonstrated the stability of the five materials in 300 K. The electronic structure calculation shows that the organic perovskite materials have wide band gap with the value of about 7.05 eV. The VBM(Valence Band Maximum) and CBM (Conduction Band Minimum) are occupied by different elements, which is conductive to the separation of electrons and holes. We found that organic cations have an important contribution to the spontaneous polarization of materials, with the contributing over 50%. The presence of hydrogen atoms in the substituting groups (MDABCO, ODABCO) enhances the hydrogen bond interaction between the organic cations and PF6-and increases the displacement of the organic cation, resulting in an increase in the contribution of the polarization of the organic cation to the total polarization. In addition, we observed large piezoelectric strain components, the calculated d33 is 36.5 pC/N for CNDABCO-NH4-(PF6)3, 32.3pC/N for SHNDABCO-NH4-(PF6)3, which is larger than the known d33 of MDABCO-NH4-I3(14pC/N). The calculated d14 is 57.5 pC/N for ODABCO-NH4-(PF6)3, 27.5 pC/N for NODABCO-NH4-(PF6)3. These components are at a high level among known organic perovskite materials and comparable to many known inorganic crystals. The large value of d14 is found to be closely related with the large value of elastic compliance tensor s44. The analysis of Young’s modulus and bulk’s modulus found that these organic perovskite materials have good ductility. These results show that these organic materials are excellent candidates for future environmentally friendly piezoelectric materials.
-
Keywords:
- Metal-free perovskites /
- first-principles calculations /
- piezoelectricity /
- spontaneous polarization
-
[1] Kieslich G, Sun S J, Cheetham A K 2014 Chem. Sci. 5 4712
[2] Sessolo M, Bolink H J 2011 Adv. Mater. 23 1829
[3] Bechmann R 2005 J. Acoust. Soc. Am. 28 347
[4] Haertling G H 1999 J. Am. Cera. Soc. 82 797
[5] Zhao Y X, Zhu K 2016 Chem. Soc. Rev. 45 655
[6] Mischenko A S, Zhang Q, Scott J F, Whatmore R W, Mathur N D 2006 Science 311 1270
[7] Peña M A, Fierro J 2001 Chem. Rev. 101 1981
[8] Zheng L L, Qi S C, Wang C M, Shi L 2019 Acta Phys. Sin. 68 147701(in Chinese) [郑隆立,齐世超,王春明,石磊,2019 物理学报 68 147701]
[9] NEATEN J B, EDERER C, WAGHMARE U V, SPALDIN N A, RABE K M 2005 Phys. Rev. B 71 14111
[10] Lebeugle D, Colson D, Forget A, Viret M 2007 Appl. Phys. Lett. 91 22907
[11] Palkar V R, Kundaliya D C, Malik S K 2003 J. Appl. Phys. 93 4337
[12] Gao W X, Chang L, Ma H, You L, Yin J, Liu J M, Liu Z G, Wang J L, Yuan G L 2015 NPG Asia Mater. 7 e189
[13] Xu W J, Kopyl S, Kholkin A, Rocha J 2019 Coordin. Chem. Rev. 387 398
[14] Nandi P, Topwal D, Park N G, Shin H 2020 J. Phys. D: Appl. Phys. 53 493002
[15] Köhnen E, Jost M, Morales-Vilches A B, Tockhorn P, Al-Ashouri A, Macco B, Kegelmann L, Korte L, Rech B, Schlatmann R, Stannowski B, Albrecht S 2019 Sustain. Energ. Fuels 3 1995
[16] Sahli F, Werner J, Kamino B A, Bräuninger M, Monnard R, Paviet-Salomon B, Barraud L, Ding L, Diaz Leon J J, Sacchetto D, Cattaneo G, Despeisse M, Boccard M, Nicolay S, Jeangros Q, Niesen B, Ballif C 2018 Nat. Mater. 17 820
[17] Yang W S, Park B, Jung E H, Jeon N J, Kim Y C, Lee D U, Shin S S, Seo J, Kim E K, Noh J H, Seok S I 2017 Science 356 1376
[18] Yun J S, Park C K, Jeong Y H, Cho J H, Paik J, Yoon S H, Hwang K 2016 Nanomater. Nanotechno. 6 20
[19] Ye H Y, Tang Y Y, Li P F, Liao W Q, Gao J X, Hua X N, Cai H, Shi P P, You Y M, Xiong R G 2018 Science 361 151
[20] Fu D W, Cai H L, Liu Y M, Ye Q, Zhang W, Zhang Y, Chen X Y, Giovannetti G, Capone M, Li J Y, Xiong R G 2013 Science 339 425
[21] Wang H, Liu H H, Zhang Z Y, Liu Z H, Lv Z L, Li T W, Ju W W, Li H S, Cai X W, Han H 2019 npj Comput. Mater 5 1
[22] Wu H S, Wei S, Chen S W, Pan H C, Pan W P, Huang S, Tsai M, Yang P 2022 Adv. Sci. 9 2105974
[23] Choi H S, Li S N, Park I, Liew W H, Zhu Z Y, Kwon K C, Wang L, Oh I, Zheng S S, Su C L, Xu Q H, Yao K, Pan F, Loh K P 2022 Nat. Commun. 13 794
[24] Sun M J, Zheng C, Gao Y, Johnston A, Najarian A M, Wang P X, Voznyy O, Hoogland S, Sargent E H 2021 Adv. Mater. 33 2006368
[25] Kasel T W, Deng Z Y, Mroz A M, Hendon C H, Butler K T, Canepa P 2019 Chem. Sci. 10 8187
[26] Kresse, Furthmuller 1996 Phys. Rev. B 54 11169
[27] Kresse, Hafner 1994 Phys. Review. B 49 14251
[28] Kresse, Hafner 1993 Phys. Review. B 47 558
[29] Spaldin N A 2012 J. Solid State Chem. 195 2
[30] Li Z Z, Li Z H, Peng G Q, Shi C, Wang H X, Ding S Y, Wang Q, Liu Z T, Jin Z W 2023 Adv. Mater. 35 2300480
[31] King-Smith R D, Vanderbilt D 1993 Phys. Rev. B 48 4442
[32] Vanderbilt D, King-Smith R D 1993 Phys. Rev. B 47 1651
[33] Wang X M, Yan Y F 2022 arXiv:2206.11137v1[cond-mat.mtrl-sci]
[34] Singh J, Kaur H, Singh G, Tripathi S K 2021 Mater. Today Energy 21 100820
[35] Al-Qaisi S, Rai D P, Haq B U, Ahmed R, Vu T V, Khuili M, Tahir S A, Alhashim H H 2021 Mater. Chem. Phys. 258 123945
[36] Kiely E, Zwane R, Fox R, Reilly A M, Guerin S 2021 CrystEngComm 23 5697
[37] Mouhat F, Coudert F 2014 Phys. Rev. B 90 224104
[38] Haid S, Bouadjemi B, Houari M, Matougui M, Lantri T, Bentata S, Aziz Z 2019 Solid State Commun. 294 29
[39] Birch F 1938 J. Appl. Phys. 9 279
[40] Kholil M I, Bhuiyan M T H 2020 Solid State Commun. 322 114053
[41] Crisler D F, Cupal J J, Moore A R 1968 P. IEEE 56 225
[42] Weis R S, Gaylord T K 1985 Appl. Phys. A 37 191
[43] Joffe H, Berlincourt D, Krueger H, Shiozawa L 1960 14th Annual Symposium on Frequency Control Atlantic City, NJ, USA May 21-June 2 1960 p19
[44] Vanderbilt D, Hamann D R, Wu X F 2005 Phys. Rev. B 72 35105
[45] X Y H 1991 Ferroelectric materials and their applications (Netherlands: Amsterdam)
[46] Li F L, Tian S W, Wu G D, Jiang C, Wu F P, Zhao X 2019 Symposium on Piezoelectrcity, Acoustic Waves and Device Applications Shijiazhuang, China, November 1-4, 2019 p1
[47] Guy I L, Muensit S, Goldys E M 1999 Appl. Phys. Lett. 75 4133
[48] Irzhak D, Roshchupkin D, Fahrtdinov R 2012 Proceedings of ISAF-ECAPD-PFM 2012 Aveiro, Portugal, July 9-13 2012 p1
Metrics
- Abstract views: 120
- PDF Downloads: 4
- Cited By: 0