Strong ferroelectricity in one-dimensional materials self-assembled by superatomic metal halide clusters

Abstract

Cluster-assembled materials have long been pursued as they can create some unprecedented and desirable properties. Herein, we assemble a class of one-dimensional (1D) ReNX₄ (X = F, Cl, Br and I) and MF₅ (M = V, Nb and Ta) nanowires by covalently linking their superatomic clusters. These assembled 1D nanowires exhibit outstanding energetic and dynamic stabilities, and hold sizable spontaneous polarization, low ferroelectric switching barriers and high critical temperature. Their superior ferroelectricity is originated from d⁰-configuration transition metal ions generated by the hybridization of empty d orbitals of metal atoms and p orbitals of non-metal atoms. These critical insights pave a new avenue to fabricate 1D ferroelectrics toward the development of miniaturized and high-density electronic devices using building blocks as cluster with precise structures and functionalities.

Graphical abstract

Keywords

ferroelectricity / superatom / cluster-assembled materials / electronic properties / first-principles calculations

References

[1] K.ZhangC. WangM.ZhangZ.BaiF.F. Xie Y.Z. TanY. GuoK.J. HuL.CaoS.Zhang X.TuD.Pan L.KangJ. ChenP.WuX.WangJ.Wang J.LiuY. SongG.WangF.SongW.Ji S.Y. XieS. F. ShiM.A. ReedB.Wang, A Gd@C82 single-molecule electret, Nat. Nanotechnol. 15(12), 1019 (2020)

[2] J. Müller, T. Böscke, D. Bräuhaus, U. Schröder, U. Böttger, J. Sundqvist, P. Kücher, T. Mikolajick, and L. Frey, Ferroelectric Zr_0.5Hf_0.5O₂ thin films for nonvolatile memory applications, Appl. Phys. Lett. 99(11), 112901 (2011)

[3] M.SiA.K. Saha S.GaoG. QiuJ.QinY.DuanJ.Jian C.NiuH. WangW.WuS.K. GuptaP.D. Ye, A ferroelectric semiconductor field-effect transistor, Nat. Electron. 2(12), 580 (2019)

[4] P. Muralt, Ferroelectric thin films for micro-sensors and actuators: A review, J. Micromech. Microeng. 10(2), 136 (2000)

[5] J. Li, S. Hou, Y. R. Yao, C. Zhang, Q. Wu, H. C. Wang, H. Zhang, X. Liu, C. Tang, M. Wei, W. Xu, Y. Wang, J. Zheng, Z. Pan, L. Kang, J. Liu, J. Shi, Y. Yang, C. J. Lambert, S. Y. Xie, and W. Hong, Room-temperature logic-in-memory operations in single-metallofullerene devices, Nat. Mater. 21(8), 917 (2022)

[6] L. W. Martin and A. M. Rappe, Thin-film ferroelectric materials and their applications, Nat. Rev. Mater. 2(2), 16087 (2016)

[7] M. Wu and P. Jena, The rise of two-dimensional van der Waals ferroelectrics, Wiley Interdiscip. Rev. Comput. Mol. Sci. 8(5), e1365 (2018)

[8] C. C. Chiang, V. Ostwal, P. Wu, C. S. Pang, F. Zhang, Z. Chen, and J. Appenzeller, Memory applications from 2D materials, Appl. Phys. Rev. 8(2), 021306 (2021)

[9] L. Qi, S. Ruan, and Y. J. Zeng, Review on recent developments in 2D ferroelectrics: Theories and applications, Adv. Mater. 33(13), 2005098 (2021)

[10] S. Horiuchi and Y. Tokura, Organic ferroelectrics, Nat. Mater. 7(5), 357 (2008)

[11] Y. Tokura, S. Koshihara, N. Iwasawa, and G. Saito, Domain-wall dynamics in organic charge-transfer compounds with one-dimensional ferroelectricity, Phys. Rev. Lett. 63(21), 2405 (1989)

[12] B. Gorshunov, V. Torgashev, E. Zhukova, V. Thomas, M. Belyanchikov, C. Kadlec, F. Kadlec, M. Savinov, T. Ostapchuk, J. Petzelt, J. Prokleška, P. V. Tomas, E. V. Pestrjakov, D. A. Fursenko, G. S. Shakurov, A. S. Prokhorov, V. S. Gorelik, L. S. Kadyrov, V. V. Uskov, R. K. Kremer, and M. Dressel, Incipient ferroelectricity of water molecules confined to nano-channels of beryl, Nat. Commun. 7(1), 12842 (2016)

[13] B. A. Hernandez, K. S. Chang, E. R. Fisher, and P. K. Dorhout, Sol−gel template synthesis and characterization of BaTiO₃ and PbTiO₃ nanotubes, Chem. Mater. 14(2), 480 (2002)

[14] P. Jena and Q. Sun, Super atomic clusters: Design rules and potential for building blocks of materials, Chem. Rev. 118(11), 5755 (2018)

[15] J. Zhao, Q. Du, S. Zhou, and V. Kumar, Endohedrally doped cage clusters, Chem. Rev. 120(17), 9021 (2020)

[16] Z. Luo and A. W. Castleman, Special and general superatoms, Acc. Chem. Res. 47(10), 2931 (2014)

[17] B. Choi, K. Lee, A. Voevodin, J. Wang, M. L. Steigerwald, P. Batail, X. Zhu, and X. Roy, Two-dimensional hierarchical semiconductor with addressable surfaces, J. Am. Chem. Soc. 140(30), 9369 (2018)

[18] E. J. Telford, J. C. Russell, J. R. Swann, B. Fowler, X. Wang, K. Lee, A. Zangiabadi, K. Watanabe, T. Taniguchi, C. Nuckolls, P. Batail, X. Zhu, J. A. Malen, C. R. Dean, and X. Roy, Doping-induced superconductivity in the van der Waals superatomic crystal Re₆Se₈Cl₂, Nano Lett. 20(3), 1718 (2020)

[19] X. Zhong, K. Lee, B. Choi, D. Meggiolaro, F. Liu, C. Nuckolls, A. Pasupathy, F. De Angelis, P. Batail, X. Roy, and X. Zhu, Superatomic two-dimensional semiconductor, Nano Lett. 18(2), 1483 (2018)

[20] X. Roy, C. H. Lee, A. C. Crowther, C. L. Schenck, T. Besara, R. A. Lalancette, T. Siegrist, P. W. Stephens, L. E. Brus, P. Kim, M. L. Steigerwald, and C. Nuckolls, Nanoscale atoms in solid-state chemistry, Science 341(6142), 157 (2013)

[21] Y. Guo, Q. Du, P. Wang, S. Zhou, J. Zhao, and Two-dimensional oxides assembled by M₄ clusters (M= B,Mo, and Te), Phys. Rev. Res. 3(4), 043231 (2021)

[22] Q. Du, Z. Wang, S. Zhou, J. Zhao, and V. Kumar, Searching for cluster Lego blocks for three-dimensional and two-dimensional assemblies, Phys. Rev. Mater. 5(6), 066001 (2021)

[23] X. Chen, G. Fei, Y. Song, T. Ying, D. Huang, B. Pan, D. Yang, X. Yang, K. Chen, X. Zhan, J. Wang, Q. Zhang, Y. Li, L. Gu, H. Gou, X. Chen, S. Li, J. Cheng, X. Liu, H. Hosono, J. Guo, and X. Chen, Superatomic-charge-density-wave in cluster-assembled Au₆Te₁₂Se₈ superconductors, J. Am. Chem. Soc. 144(45), 20915 (2022)

[24] S. Xing, L. Wu, Z. Wang, X. Chen, H. Liu, S. Han, L. Lei, L. Zhou, Q. Zheng, L. Huang, X. Lin, S. Chen, L. Xie, X. Chen, H. J. Gao, Z. Cheng, J. Guo, S. Wang, and W. Ji, Interweaving polar charge orders in a layered metallic superatomic crystal, Phys. Rev. X 12(4), 041034 (2022)

[25] Y. Zhao, Y. Guo, Y. Qi, X. Jiang, Y. Su, and J. Zhao, Coexistence of ferroelectricity and ferromagnetism in fullerene-based one-dimensional chains, Adv. Sci. (Weinh.) 10(21), 2301265 (2023)

[26] J. R. Dilworth, Rhenium chemistry – then and now, Coord. Chem. Rev. 436, 213822 (2021)

[27] K.DehnickeJ. Straehle, N-Halogenoimido complexes of transition metals, Chem. Rev. 93(3), 981 (1993)

[28] W. Liese, K. Dehnicke, I. Walker, J. Strähle, and Darstellung und kristallstruktur von rhenium (VII)-nitridchlorid, ReNCl₄, Z. Naturforsch. B. J. Chem. Sci. 34(5), 693 (1979)

[29] G. Kresse and J. Furthmüller, Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set, Phys. Rev. B 54(16), 11169 (1996)

[30] G. Kresse and D. Joubert, From ultrasoft pseudopotentials to the projector augmented-wave method, Phys. Rev. B 59(3), 1758 (1999)

[31] J. P. Perdew, K. Burke, and M. Ernzerhof, Generalized gradient approximation made simple, Phys. Rev. Lett. 77(18), 3865 (1996)

[32] J. Heyd, G. E. Scuseria, and M. Ernzerhof, Hybrid functionals based on a screened Coulomb potential, J. Chem. Phys. 118(18), 8207 (2003)

[33] S. Baroni, S. de Gironcoli, A. Dal Corso, and P. Giannozzi, Phonons and related crystal properties from density-functional perturbation theory, Rev. Mod. Phys. 73(2), 515 (2001)

[34] R. Krishnan, J. S. Binkley, R. Seeger, and J. A. Pople, Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions, J. Chem. Phys. 72(1), 650 (1980)

[35] M. Dolg, U. Wedig, H. Stoll, and H. Preuss, Energy‐adjusted ab initio pseudopotentials for the first row transition elements, J. Chem. Phys. 86(2), 866 (1987)

[36] M.FrischG. TrucksH.SchlegelG.ScuseriaM.Robb J.CheesemanG. ScalmaniV.BaroneG.PeterssonH.Nakatsuji, Gaussian 16, Revision A. 03, Gaussian, Inc. Wallingford CT 3 (2016)

[37] T. Tsukamoto, N. Haruta, T. Kambe, A. Kuzume, and K. Yamamoto, Periodicity of molecular clusters based on symmetry-adapted orbital model, Nat. Commun. 10(1), 3727 (2019)

[38] G.HenkelmanA. ArnaldssonH.Jónsson, A fast and robust algorithm for Bader decomposition of charge density, Comput. Mater. Sci. 36(3), 354 (2006)

[39] M. Segall, R. Shah, C. J. Pickard, and M. Payne, Population analysis of plane-wave electronic structure calculations of bulk materials, Phys. Rev. B 54(23), 16317 (1996)

[40] D. Xiao, M. C. Chang, and Q. Niu, Berry phase effects on electronic properties, Rev. Mod. Phys. 82(3), 1959 (2010)

[41] E. Bruyer, D. Di Sante, P. Barone, A. Stroppa, M. H. Whangbo, S. Picozzi, Possibility of combining ferroelectricity, Rashba-like spin splitting in monolayers of the 1T-type transition-metal dichalcogenides MX₂ (M= Mo, and W; X= S, Te), Phys. Rev. B 94(19), 195402 (2016)

[42] R. Fei, W. Kang, and L. Yang, Ferroelectricity and phase transitions in monolayer group-IV monochalcogenides, Phys. Rev. Lett. 117(9), 097601 (2016)

[43] W. Wan, C. Liu, W. Xiao, and Y. Yao, Promising ferroelectricity in 2D group IV tellurides: A first-principles study, Appl. Phys. Lett. 111(13), 132904 (2017)

[44] R. E. Cohen, Origin of ferroelectricity in perovskite oxides, Nature 358(6382), 136 (1992)

[45] K. J. Choi, M. Biegalski, Y. L. Li, A. Sharan, J. Schubert, R. Uecker, P. Reiche, Y. B. Chen, X. Q. Pan, V. Gopalan, L. Q. Chen, D. G. Schlom, and C. B. Eom, Enhancement of ferroelectricity in strained BaTiO₃ thin films, Science 306(5698), 1005 (2004)

[46] J. Rouquette, J. Haines, V. Bornand, M. Pintard, P. Papet, W. G. Marshall, and S. Hull, Pressure-induced rotation of spontaneous polarization in monoclinic and triclinic PbZr_0.52Ti_0.48O₃, Phys. Rev. B 71(2), 024112 (2005)

[47] N. Izyumskaya, Y. I. Alivov, S. J. Cho, H. Morkoç, H. Lee, and Y. S. Kang, Processing, structure, properties, and applications of PZT thin films, Crit. Rev. Solid State Mater. Sci. 32(3−4), 111 (2007)

[48] I.Bersuker, The Jahn−Teller Effect and Vibronic Interactions in Modern Chemistry, Springer Science & Business Media: 2013

[49] J. van den Brink and D. I. Khomskii, Multiferroicity due to charge ordering, J. Phys.: Condens. Matter 20(43), 434217 (2008)

[50] Y. Bao and F. Zhang, Electronic engineering of ABO₃ perovskite metal oxides based on d⁰ electronic-configuration metallic ions toward photocatalytic water splitting under visible light, Small Struct. 3(6), 2100226 (2022)

[51] J. C. Wojdeł and J. Íñiguez, Testing simple predictors for the temperature of a structural phase transition, Phys. Rev. B 90(1), 014105 (2014)

[52] G. Kresse and J. Hafner, Ab initio molecular dynamics for liquid metals, Phys. Rev. B 47(1), 558 (1993)

[53] K. A. N. Duerloo, M. T. Ong, and E. J. Reed, Intrinsic piezoelectricity in two-dimensional materials, J. Phys. Chem. Lett. 3(19), 2871 (2012)

[54] K. M. Ok, E. O. Chi, and P. S. Halasyamani, Bulk characterization methods for non-centrosymmetric materials: Second-harmonic generation, piezoelectricity, pyroelectricity, and ferroelectricity, Chem. Soc. Rev. 35(8), 710 (2006)

Declarations

The authors declare that they have no competing interests and there are no conflicts.

Electronic supplementary materials

The online version contains supplementary material available at https://doi.org/10.1007/s11467-024-1434-3 and https://journal.hep.com.cn/fop/EN/10.1007/s11467-024-1434-3.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 12004065, 91961204, 12222403, and 11974068), the Doctoral Start-up Foundation of Liaoning Province (No. 2022-BS-081), and the Fundamental Research Funds for the Central Univeristies (No. DUT24LAB114).

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