Citation: ZHANG Chunmei, NIE Yihan, DU Aijun. Intrinsic Ultrahigh Negative Poisson's Ratio in Two-Dimensional Ferroelectric ABP₂X₆ Materials[J]. Acta Physico-Chimica Sinica, ;2019, 35(10): 1128-1133. doi: 10.3866/PKU.WHXB201812037 shu

Intrinsic Ultrahigh Negative Poisson's Ratio in Two-Dimensional Ferroelectric ABP₂X₆ Materials

School of Chemistry, Physics and Mechanical Engineering, Queensland University of Technology, Gardens Point Campus, Brisbane, QLD 4001, Australia

Corresponding author: DU Aijun, aijun.du@qut.edu.au
Received Date: 21 December 2018
Revised Date: 24 January 2019
Accepted Date: 24 January 2019
Available Online: 28 October 2019
Fund Project: D.A. acknowledges the financial support by Australian Research Council under Discovery Project DP170103598D.A. acknowledges the financial support by Australian Research Council under Discovery Project (DP170103598)

Recently, ferroelectric materials have attracted considerable research attention. In particular, two dimensional (2D) ferroelectric materials have been considered as most crucial for next-generation circuit designs because of their application as novel electric memory devices. However, a 2D ferroelectric material is very rare. The ferroelectric materials with the form ABP₂X₆ (A = Ag, Cu; B = Bi, In; X = S, Se) are of interest because of their ferroelectric property maintained in their ultrathin structures. Within the ABP₂X₆ monolayer, the P―P bonds form the pillars that hold the top and bottom X planes, while the off-center A―B atoms between the X layers induce a spontaneous ferroelectric polarization. If the two off-center A―B sites are equally aligned, this would lead to the appearance of the paraelectric state. Such intriguing structures must impart novel mechanical properties to the materials. Until now, there has been no report on the mechanical properties of monolayer ABP₂X₆. Based on ﬁrst-principles calculations, we studied the structural, electronic, mechanical as well as the electromechanical coupling properties of monolayer ABP₂X₆ (A = Ag, Cu; B = Bi, In; X = S, Se). We found that they are all semiconductors with wide bandgaps of 2.73, 2.17, 3.00, and 2.31 eV for CuInP₂Se₆, CuBiP₂Se₆, AgBiP₂S₆, and AgBiP₂Se₆, respectively, which are calculated based on the Heyd-Scuseria-Ernzerhof (HSE) exchange correlation functional model. The conduction band minimum is mainly from p orbitals of X and B atoms, whereas the valence band maximum is due to the hybridization of the p orbital of X atoms and the d orbital of A atoms. Moreover, there are three short and three long A/B―X bonds due to the A―B off-center displacement. Together with the d-p orbital hybridization, the main reason for the distorted ferroelectric structure in ABP₂X₆ monolayers is the Jahn-Teller effect. ABP₂X₆ monolayers are predicted to be a new class of auxetic materials with an out-of-plane negative Poisson's ratio, i.e., the values of the negative Poisson's ratio are in the order AgBiP₂S₆ (−0.805) < AgBiP₂Se₆ (−0.778) < CuBiP₂Se₆ (−0.670) < CuInP₂S₆ (−0.060). This is mainly due to the tensile strain applied in the x/y direction enlarging the angle between P―P bonds and top layer X atoms, thereby enhancing the bucking height of monolayer ABP₂X₆. Moreover, external strain has a significant impact on the A―B off-center displacement, rendering an out-of-plane piezoelectric polarization. The values of e₁₃ for CuInP₂S₆, CuBiP₂Se₆, AgBiP₂S₆, AgBiP₂Se₆ monolayers are calculated to be −3.95 × 10⁻¹², −5.68 × 10⁻¹², −3.94 × 10⁻¹², −2.71 × 10⁻¹² C∙m⁻¹, respectively, which are comparable to the only experimentally confirmed 2D out-of-plane piezoelectric Janus system (piezoelectric coefficient = −3.8 × 10⁻¹² C∙m⁻¹). This unusual auxetic behavior, ferroelectric polarization, and the electromechanical coupling in monolayer ABP₂X₆ could potentially lead to enormous technologically important applications in nanoelectronics, nanomechanics, and piezoelectrics.
- Negative poisson's ratio,
- Ferroelectric,
- Semiconductor,
- ABP₂X₆,
- Mechanical,
- Piezoelectric
1. [1]
  Evans, K. E.; Alderson, A. Adv. Mater. 2000, 12, 617. doi: 10.1002/(SICI)1521-4095(200005)12:9<617::AID-ADMA617 >3.0.CO;2-3 doi: 10.1002/(SICI)1521-4095(200005)12:9<617::AID-ADMA617>3.0.CO;2-3
2. [2]
  Dagdelen, J.; Montoya, J.; de Jong, M.; Persson, K. Nat. Commun. 2017, 8, 323. doi: 10.1038/s41467-017-00399-6 doi: 10.1038/s41467-017-00399-6
3. [3]
  Wang, Y.; Li, F.; Li, Y.; Chen, Z. Nat. Commun. 2016, 7, 11488. doi: 10.1038/ncomms11488 doi: 10.1038/ncomms11488
4. [4]
  Jiang, J. W.; Park, H. S. Nat. Commun. 2014, 5, 4727. doi: 10.1038/ncomms5727 doi: 10.1038/ncomms5727
5. [5]
  Wang, H.; Li, X.; Sun, J.; Liu, Z.; Yang, J. 2D Mater. 2017, 4, 045020. doi: 10.1088/2053-1583/aa8abd doi: 10.1088/2053-1583/aa8abd
6. [6]
  Zhang, L. C.; Qin, G.; Fang, W. Z.; Cui, H. J.; Zheng, Q. R.; Yan, Q. B.; Su, G. Sci. Rep. 2016, 6, 19830. doi: 10.1038/srep19830 doi: 10.1038/srep19830
7. [7]
  Zhang, S.; Zhou, J.; Wang, Q.; Chen, X.; Kawazoe, Y.; Jena, P. Proc. Natl. Acad. Sci. USA 2015, 112, 2372. doi: 10.1073/pnas.1416591112 doi: 10.1073/pnas.1416591112
8. [8]
  Gao, Z.; Dong, X.; Li, N.; Ren, J. Nano Lett. 2017, 17, 772. doi: 10.1021/acs.nanolett.6b03921 doi: 10.1021/acs.nanolett.6b03921
9. [9]
  Wang, H.; Li, Q.; Gao, Y.; Miao, F.; Zhou, X. F.; Wan, X. New J. Phy. 2016, 18, 073016. doi: 10.1088/1367-2630/18/7/073016 doi: 10.1088/1367-2630/18/7/073016
10. [10]
  Kou, L.; Ma, Y.; Tang, C.; Sun, Z.; Du, A.; Chen, C. Nano Lett. 2016, 16, 7910. doi: 10.1021/acs.nanolett.6b04180 doi: 10.1021/acs.nanolett.6b04180
11. [11]
  Zhou, L.; Zhuo, Z.; Kou, L.; Du, A.; Tretiak, S. Nano Lett. 2017, 17, 4466. doi:10.1021/acs.nanolett.7b01704 doi: 10.1021/acs.nanolett.7b01704
12. [12]
  Zhang, C.; Jiao, Y.; He, T.; Bottle, S.; Frauenheim, T.; Du, A. J. Phys. Chem. Lett. 2018, 9, 858. doi: 10.1021/acs.jpclett.7b03449 doi: 10.1021/acs.jpclett.7b03449
13. [13]
  Wang, B.; Yuan, S.; Li, Y.; Shi, L.; Wang, J. Nanoscale 2017, 9, 5577. doi: 10.1039/C7NR00455A doi: 10.1039/C7NR00455A
14. [14]
  Huang, C.; Du, Y.; Wu, H.; Xiang, H.; Deng, K.; Kan, E. Phys. Rev. Lett. 2018, 120, 147601. doi: 10.1103/Phys. Rev. Lett.120.147601 doi: 10.1103/Phys.Rev.Lett.120.147601
15. [15]
  Zhang, C.; Nie, Y.; Sanvito, S.; Du, A. Nano Lett. 2019, doi: 10.1021/acs.nanolett.8b05050 doi: 10.1021/acs.nanolett.8b05050
16. [16]
  Maisonneuve, V.; Cajipe, V.; Simon, A.; Von Der Muhll, R.; Ravez, J. Phys. Rev. B 1997, 56, 10860. doi: 10.1103/PhysRevB.56.10860 doi: 10.1103/PhysRevB.56.10860
17. [17]
  Gave, M. A.; Bilc, D.; Mahanti, S.; Breshears, J. D.; Kanatzidis, M. G. Inorg. Chem. 2005, 44, 5293. doi: 10.1021/ic050357+ doi: 10.1021/ic050357+
18. [18]
  Reimers, J. R.; Tawfik, S. A.; Ford, M. J. Chem. Sci. 2018, 9, 7620. doi: 10.1039/C8SC01274A doi: 10.1039/C8SC01274A
19. [19]
  Liu, F.; You, L.; Seyler, K. L.; Li, X.; Yu, P.; Lin, J.; Wang, X.; Zhou, J.; Wang, H.; He, H. Nat. Commun. 2016, 7, 12357. doi: 10.1038/ncomms12357 doi: 10.1038/ncomms12357
20. [20]
  Song, W.; Fei, R.; Yang, L. Phys. Rev. B 2017, 96, 235420. doi: 10.1103/PhysRevB.96.235420 doi: 10.1103/PhysRevB.96.235420
21. [21]
  Xu, B.; Xiang, H.; Xia, Y.; Jiang, K.; Wan, X.; He, J.; Yin, J.; Liu, Z. Nanoscale 2017, 9, 8427. doi:10.1039/C7NR02461D doi: 10.1039/C7NR02461D
22. [22]
  Lai Y., Song Z., Wan Y., Xue M., Ye Y., Dai L., Yang W., Du H. arXiv preprint arXiv: 1805.04280 2018.
23. [23]
  Shirodkar, S. N.; Waghmare, U. V. Phys. Rev. Lett. 2014, 112, 157601. doi: 10.1103/PhysRevLett.112.157601 doi: 10.1103/PhysRevLett.112.157601
24. [24]
  Fei, R.; Kang, W.; Yang, L. Phys. Rev. Lett. 2016, 117, 097601. doi: 10.1103/PhysRevLett.117.097601 doi: 10.1103/PhysRevLett.117.097601
25. [25]
  Yu, L.; Yan, Q.; Ruzsinszky, A. Nat. Commun. 2017, 8, 15224. doi: 10.1038/ncomms15224 doi: 10.1038/ncomms15224
26. [26]
  Wu, M.; Zeng, X. C. Nano Lett. 2016, 16, 3236. doi: 10.1021/acs.nanolett.6b00726 doi: 10.1021/acs.nanolett.6b00726
27. [27]
  Kresse, G.; Furthmüller, J. Comp. Mater. Sci. 1996, 6, 15. doi: 10.1016/0927-0256(96)00008-0 doi: 10.1016/0927-0256[96]00008-0
28. [28]
  Kresse, G.; Furthmüller, J. Phy. Rev. B 1996, 54, 11169. doi: 10.1103/PhysRevB.54.11169 doi: 10.1103/PhysRevB.54.11169
29. [29]
  Blöchl, P. E. Phy. Rev. B 1994, 50, 17953. doi: 10.1103/PhysRevB.50.17953 doi: 10.1103/PhysRevB.50.17953
30. [30]
  Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996, 77, 3865. doi:10.1103/PhysRevLett.77.3865 doi: 10.1103/PhysRevLett.77.3865
31. [31]
  Heyd, J.; Scuseria, G. E.; Ernzerhof, M. J. Chem. Phys. 2003, 118, 8207. doi:10.1063/1.1564060 doi: 10.1063/1.1564060
32. [32]
  Grimme, S. J. Comput. Chem. 2006, 27, 1787. doi: 10.1002/jcc.20495 doi: 10.1002/jcc.20495
33. [33]
  King-Smith, R.; Vanderbilt, D. Phys. Rev. B 1993, 47, 1651. doi: 10.1103/PhysRevB.47.1651 doi: 10.1103/PhysRevB.47.1651
34. [34]
  Zhang, C.; Kou, L.; He, T.; Jiao, Y.; Liao, T.; Bottle, S.; Du, A. Computat. Mater. Sci. 2018, 149, 158. doi: 10.1016/j.commatsci.2018.03.027 doi: 10.1016/j.commatsci.2018.03.027
35. [35]
  Zhang, C.; Jiao, Y.; Ma, F.; Bottle, S.; Zhao, M.; Chen, Z.; Du, A. Phys. Chem. Chem. Phys. 2017, 19, 5449. doi: 10.1039/C7CP00157F doi: 10.1039/C7CP00157F
36. [36]
  Zhang, C.; Jiao, Y.; He, T.; Ma, F.; Kou, L.; Liao, T.; Bottle, S.; Du, A. Phys. Chem. Chem. Phys. 2017, 19, 25886. doi: 10.1039/C7CP04758D doi: 10.1039/C7CP04758D
37. [37]
  Zhang, C.; Du, A. Beilstein J. Nanotechnol. 2018, 9, 1399. doi: 10.3762/bjnano.9.132 doi: 10.3762/bjnano.9.132
38. [38]
  Zhang, C.; Nie, Y.; Liao, T.; Kou, L.; Du, A. Phys. Rev. B 2019, 99, 035424. doi:10.1103/PhysRevB.99.035424 doi: 10.1103/PhysRevB.99.035424
39. [39]
  Wei, S. H.; Zhang, S.; Zunger, A. Phys. Rev. Lett. 1993, 70, 1639. doi: 10.1103/PhysRevLett.70.1639 doi: 10.1103/PhysRevLett.70.1639
40. [40]
  Wu, W.; Wang, L.; Li, Y.; Zhang, F.; Lin, L.; Niu, S.; Chenet, D.; Zhang, X.; Hao, Y.; Heinz, T. F. Nature 2014, 514, 470. doi: 10.1038/nature13792 doi: 10.1038/nature13792
41. [41]
  Lu, A. Y.; Zhu, H.; Xiao, J.; Chuu, C. P.; Han, Y.; Chiu, M. H.; Cheng, C. C.; Yang, C. W.; Wei, K. H.; Yang, Y. Nat. Nanotechnol. 2017, 12, 744. doi: 10.1038/nnano.2017.100 doi: 10.1038/nnano.2017.100
42. [42]
  Li, R.; Cheng, Y.; Huang, W. Small 2018, 14, 1802091. doi: 10.1002/smll.201802091 doi: 10.1002/smll.201802091
1. [1]
  Zheng Zhang , Lei Shi , Bin Wang , Jingyuan Qu , Xiaoling Wang , Tao Wang , Qitao Jiang , Wuhong Xue , Xiaohong Xu . Epitaxial growth of full-vdW α-In₂Se₃/MoS₂ heterostructures for all-in-one sensing and memory-computing artificial visual system. Chinese Chemical Letters, 2025, 36(3): 109687-. doi: 10.1016/j.cclet.2024.109687
2. [2]
  Xin Jiang , Han Jiang , Yimin Tang , Huizhu Zhang , Libin Yang , Xiuwen Wang , Bing Zhao . g-C₃N₄/TiO_2-X heterojunction with high-efficiency carrier separation and multiple charge transfer paths for ultrasensitive SERS sensing. Chinese Chemical Letters, 2024, 35(10): 109415-. doi: 10.1016/j.cclet.2023.109415
3. [3]
  Hao-Fei Ni , Jia-He Lin , Gele Teri , Qiang-Qiang Jia , Pei-Zhi Huang , Hai-Feng Lu , Chang-Feng Wang , Zhi-Xu Zhang , Da-Wei Fu , Yi Zhang . B-site ion regulation strategy enables performance optimization and multifunctional integration of hybrid perovskite ferroelectrics. Chinese Chemical Letters, 2025, 36(3): 109690-. doi: 10.1016/j.cclet.2024.109690
4. [4]
  Hong-Tao Ji , Yu-Han Lu , Yan-Ting Liu , Yu-Lin Huang , Jiang-Feng Tian , Feng Liu , Yan-Yan Zeng , Hai-Yan Yang , Yong-Hong Zhang , Wei-Min He . Nd@C₃N₄-photoredox/chlorine dual catalyzed synthesis and evaluation of antitumor activities of 4-alkylated sulfonyl ketimines. Chinese Chemical Letters, 2025, 36(2): 110568-. doi: 10.1016/j.cclet.2024.110568
5. [5]
  Xinghong Cai , Qiang Yang , Yao Tong , Lanyin Liu , Wutang Zhang , Sam Zhang , Min Wang . AlO₂: A novel two-dimensional material with a high negative Poisson's ratio for the adsorption of volatile organic compounds. Chinese Chemical Letters, 2025, 36(2): 109586-. doi: 10.1016/j.cclet.2024.109586
6. [6]
  Meng Lin , Hanrui Chen , Congcong Xu . Preparation and Study of Photo-Enhanced Electrocatalytic Oxygen Evolution Performance of ZIF-67/Copper(I) Oxide Composite: A Recommended Comprehensive Physical Chemistry Experiment. University Chemistry, 2024, 39(4): 163-168. doi: 10.3866/PKU.DXHX202308117
7. [7]
  Xinpin Pan , Yongjian Cui , Zhe Wang , Bowen Li , Hailong Wang , Jian Hao , Feng Li , Jing Li . Robust chemo-mechanical stability of additives-free SiO₂ anode realized by honeycomb nanolattice for high performance Li-ion batteries. Chinese Chemical Letters, 2024, 35(10): 109567-. doi: 10.1016/j.cclet.2024.109567
8. [8]
  Pei Cao , Yilan Wang , Lejian Yu , Miao Wang , Liming Zhao , Xu Hou . Dynamic asymmetric mechanical responsive carbon nanotube fiber for ionic logic gate. Chinese Chemical Letters, 2024, 35(6): 109421-. doi: 10.1016/j.cclet.2023.109421
9. [9]
  Yuqing Zhu , Haohao Chen , Li Wang , Liqun Ye , Houle Zhou , Qintian Peng , Huaiyong Zhu , Yingping Huang . Piezoelectric materials for pollutants degradation: State-of-the-art accomplishments and prospects. Chinese Chemical Letters, 2024, 35(4): 108884-. doi: 10.1016/j.cclet.2023.108884
10. [10]
  Neng Shi , Haonan Jia , Jixiang Zhang , Pengyu Lu , Chenglong Cai , Yixin Zhang , Liqiang Zhang , Nongyue He , Weiran Zhu , Yan Cai , Zhangqi Feng , Ting Wang . Accurate expression of neck motion signal by piezoelectric sensor data analysis. Chinese Chemical Letters, 2024, 35(9): 109302-. doi: 10.1016/j.cclet.2023.109302
11. [11]
  Cunjun Li , Wencong Liu , Xianlei Chen , Liang Li , Shenyu Lan , Mingshan Zhu . Adsorption and activation of peroxymonosulfate on BiOCl for carbamazepine degradation: The role of piezoelectric effect. Chinese Chemical Letters, 2024, 35(10): 109652-. doi: 10.1016/j.cclet.2024.109652
12. [12]
  Min Chen , Boyu Peng , Xuyun Guo , Ye Zhu , Hanying Li . Polyethylene interfacial dielectric layer for organic semiconductor single crystal based field-effect transistors. Chinese Chemical Letters, 2024, 35(4): 109051-. doi: 10.1016/j.cclet.2023.109051
13. [13]
  Xin He , Feng Liu , Tao Tu . Double redox-mediated intrinsic semiconductor photocatalysis: Practical semi-heterogeneous synthesis. Chinese Chemical Letters, 2025, 36(3): 110621-. doi: 10.1016/j.cclet.2024.110621
14. [14]
  Dongmei Yao , Junsheng Zheng , Liming Jin , Xiaomin Meng , Zize Zhan , Runlin Fan , Cong Feng , Pingwen Ming . Effect of surface oxidation on the interfacial and mechanical properties in graphite/epoxy composites composite bipolar plates. Chinese Chemical Letters, 2024, 35(11): 109382-. doi: 10.1016/j.cclet.2023.109382
15. [15]
  Shunshun Jiang , Ji Zhang , Jing Wang , Shan-Tao Zhang . Excellent energy storage properties in non-stoichiometric Bi_0.5Na_0.5TiO₃-based relaxor ferroelectric ceramics. Chinese Chemical Letters, 2024, 35(7): 108955-. doi: 10.1016/j.cclet.2023.108955
16. [16]
  Qinyu Zhao , Yunchao Zhao , Songjing Zhong , Zhaoyang Yue , Zhuoheng Jiang , Shaobo Wang , Quanhong Hu , Shuncheng Yao , Kaikai Wen , Linlin Li . Urchin-like piezoelectric ZnSnO₃/Cu₃P p-n heterojunction for enhanced cancer sonodynamic therapy. Chinese Chemical Letters, 2024, 35(12): 109644-. doi: 10.1016/j.cclet.2024.109644
17. [17]
  Shuangliang Xie , Yuyue Chen , Qing He , Liang Chen , Jikun Yang , Shiqing Deng , Yimei Zhu , He Qi . Relaxor antiferroelectric-relaxor ferroelectric crossover in NaNbO₃-based lead-free ceramics for high-efficiency large-capacitive energy storage. Chinese Chemical Letters, 2024, 35(7): 108871-. doi: 10.1016/j.cclet.2023.108871
18. [18]
  Xiutao Xu , Chunfeng Shao , Jinfeng Zhang , Zhongliao Wang , Kai Dai . Rational Design of S-Scheme CeO₂/Bi₂MoO₆ Microsphere Heterojunction for Efficient Photocatalytic CO₂ Reduction. Acta Physico-Chimica Sinica, 2024, 40(10): 2309031-. doi: 10.3866/PKU.WHXB202309031
19. [19]
  Qianqian Liu , Xing Du , Wanfei Li , Wei-Lin Dai , Bo Liu . Synergistic Effects of Internal Electric and Dipole Fields in SnNb₂O₆/Nitrogen-Enriched C₃N₅ S-Scheme Heterojunction for Boosting Photocatalytic Performance. Acta Physico-Chimica Sinica, 2024, 40(10): 2311016-. doi: 10.3866/PKU.WHXB202311016
20. [20]
  Mianying Huang , Zhiguang Xu , Xiaoming Lin . Mechanistic analysis of Co2VO4/X (X = Ni, C) heterostructures as anode materials of lithium-ion batteries. Chinese Journal of Structural Chemistry, 2024, 43(7): 100309-100309. doi: 10.1016/j.cjsc.2024.100309

Get Citation

PDF

XML

Metrics

PDF Downloads(10)
Abstract views(659)
HTML views(71)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Intrinsic Ultrahigh Negative Poisson's Ratio in Two-Dimensional Ferroelectric ABP2X6 Materials

Metrics

通讯作者: 陈斌, bchen63@163.com

Intrinsic Ultrahigh Negative Poisson's Ratio in Two-Dimensional Ferroelectric ABP₂X₆ Materials