Abstract
Discovering new two-dimensional (2D) materials, exploring their unique properties and potentials in various applications are of paramount importance to condensed matter physics and materials science. Here based on the diverse properties of the novel square lattice S-XS2 materials found in experiments and computations, we identified 7 novel 2D Janus S-XSSe (X = Si, Sn, V, Cr, Mo, Re, Os) monolayers by means of density functional theory computations. Remarkably, both S-SiSSe and S-SnSSe monolayers possess the auxetic behavior. In addition, they can act as potential photocatalysts, and their photocatalytic performance can be enhanced by changing the pH and applying biaxial strains. Without spin-orbit coupling (SOC), the S-VSSe, S-CrSSe, and S-MoSSe are ferromagnetic half-metals, and have high Curie temperatures TC (210, 810, and 390 K, respectively). When SOC is included, the S-VSSe becomes a quantum anomalous Hall insulator with a sizable gap (45.4 meV) and one chiral edge state (Chern number C = −1). By symmetry analysis of semiconducting S-XSSe (X = Si, Sn, V) monolayers, only out-of-plane piezoelectric response can be induced by a uniaxial strain in the basal plane, and among them, S-VSSe has both the largest out-of-plane piezoelectric coefficients d31 and d32, with values of −0.013 and 0.025 pm V−1, respectively. The concurrence of ferromagnetism, topology, and piezoelectricity empowers the S-VSSe monolayer as a potential platform for multi-functional spintronics applications with a large gap and high TC. This theoretical work brings new members, also manifoldness in the properties and functions to the renown 2D materials family.
摘要
发现新的二维材料并探索其独特性质与潜在应用是凝聚态物理 与材料科学的重要课题. 在此, 我们基于在实验和计算中报道的具有多 种性质的新型方晶格S-XS2二维材料, 通过密度泛函理论计算, 确定了 7种具有近似方晶格的新型二维Janus S-XSSe (X = Si, Sn, V, Cr, Mo, Re和Os)单层材料. 值得注意的是, S-SiSSe和S-SnSSe单层都具有拉胀行 为, 此外, 由于具有合适的带边位置、可见光区的高效吸收系数和较大 的载流子迁移率差, 它们是潜在的光催化剂, 而且光催化性能还可以通 过改变pH值和施加双轴应变来提高. 在不考虑自旋轨道耦合(SOC)时, S-VSSe, S-CrSSe和S-MoSSe是铁磁半金属, 并具有较高的居里温度TC (分别为210, 810和390 K). 加入SOC后, S-VSSe成为量子反常霍尔 (QAH)绝缘体, 具有较大的带隙(45.4 meV)和一个手性边缘态(陈数C = −1). 通过对半导体S-XSSe (X = Si, Sn, V) 单层的对称性分析, 基底面上 的单轴应变只能诱发面外压电响应. 其中, S-VSSe的面外压电系数d31和 d32最大, 分别为−0.013和0.025 pm V−1. 压电性、拓扑性和铁磁性的共 存使单层S-VSSe成为具有大带隙和高TC的多功能自旋电子学应用的潜 在平台. 我们的理论工作将给二维材料增添新家族, 并有望带来更广阔 的应用.
Article PDF
Similar content being viewed by others
References
Novoselov KS, Geim AK, Morozov SV, et al. Electric field effect in atomically thin carbon films. Science, 2004, 306: 666–669
Cooper DR, D’Anjou B, Ghattamaneni N, et al. Experimental review of graphene. ISRN Condensed Matter Phys, 2012, 2012: 1–56
Zhang Y, Tang TT, Girit C, et al. Direct observation of a widely tunable bandgap in bilayer graphene. Nature, 2009, 459: 820–823
Craciun MF, Russo S, Yamamoto M, et al. Tuneable electronic properties in graphene. Nano Today, 2011, 6: 42–60
Pacilé D, Meyer JC, Zettl A, et al. The two-dimensional phase of boron nitride: Few-atomic-layer sheets and suspended membranes. Appl Phys Lett, 2008, 92: 133107
Vogt P, De Padova P, Quaresima C, et al. Silicene: Compelling experimental evidence for graphenelike two-dimensional silicon. Phys Rev Lett, 2012, 108: 155501
Wang QH, Kalantar-Zadeh K, Kis A, et al. Electronics and optoelectronics of two-dimensional transition metal dichalcogenides. Nat Nanotech, 2012, 7: 699–712
Kuc A, Zibouche N, Heine T. Influence of quantum confinement on the electronic structure of the transition metal sulfide TS2. Phys Rev B, 2011, 83: 245213
Yuan X, Yang M, Wang L, et al. Structural stability and intriguing electronic properties of two-dimensional transition metal dichalcogenide alloys. Phys Chem Chem Phys, 2017, 19: 13846–13854
Jariwala D, Sangwan VK, Lauhon LJ, et al. Emerging device applications for semiconducting two-dimensional transition metal dichalcogenides. ACS Nano, 2014, 8: 1102–1120
Guo H, Lu N, Wang L, et al. Tuning electronic and magnetic properties of early transition-metal dichalcogenides via tensile strain. J Phys Chem C, 2014, 118: 7242–7249
Morgan JW, Anders E. Chemical composition of earth, venus, and mercury. Proc Natl Acad Sci USA, 1980, 77: 6973–6977
Zhu CR, Wang G, Liu BL, et al. Strain tuning of optical emission energy and polarization in monolayer and bilayer MoS2. Phys Rev B, 2013, 88: 121301
Raiber S, Faria Junior PE, Falter D, et al. Ultrafast pseudospin quantum beats in multilayer WSe2 and MoSe2. Nat Commun, 2022, 13: 4997
Ding Y, Wang Y, Ni J, et al. First principles study of structural, vibrational and electronic properties of graphene-like MX2 (M = Mo, Nb, W, Ta; X = S, Se, Te) monolayers. Phys B-Condensed Matter, 2011, 406: 2254–2260
Radisavljevic B, Whitwick MB, Kis A. Integrated circuits and logic operations based on single-layer MoS2. ACS Nano, 2011, 5: 9934–9938
Miller CW, Sharoni A, Liu G, et al. Quantitative structural analysis of organic thin films: An X-ray diffraction study. Phys Rev B, 2005, 72: 104113
Radisavljevic B, Radenovic A, Brivio J, et al. Single-layer MoS2 transistors. Nat Nanotech, 2011, 6: 147–150
Zhang J, Jia S, Kholmanov I, et al. Janus monolayer transition-metal dichalcogenides. ACS Nano, 2017, 11: 8192–8198
Zhu ZY, Cheng YC, Schwingenschlögl U. Giant spin-orbit-induced spin splitting in two-dimensional transition-metal dichalcogenide semiconductors. Phys Rev B, 2011, 84: 153402
Zibouche N, Kuc A, Musfeldt J, et al. Transition-metal dichalcogenides for spintronic applications. Annalen der Phys, 2014, 526: 395–401
Liu Z, Li L, Cui L, et al. Intrinsic spin-valley-coupled Dirac state in Janus functionalized β-BiAs monolayer. Nanoscale Horiz, 2021, 6: 283–289
Sattar S, Islam MF, Canali CM. Monolayer MnX and Janus XMnY (X, Y = S, Se, Te): A family of two-dimensional antiferromagnetic semiconductors. Phys Rev B, 2022, 106: 085410
Bychkov YA, Rashba EI. Oscillatory effects and the magnetic susceptibility of carriers in inversion layers. J Phys C-Solid State Phys, 1984, 17: 6039–6045
Cheng YC, Zhu ZY, Tahir M, et al. Spin-orbit-induced spin splittings in polar transition metal dichalcogenide monolayers. EPL, 2013, 102: 57001
Ma X, Wu X, Wang H, et al. A Janus MoSSe monolayer: A potential wide solar-spectrum water-splitting photocatalyst with a low carrier recombination rate. J Mater Chem A, 2018, 6: 2295–2301
Lin P, Pan C, Wang ZL. Two-dimensional nanomaterials for novel piezotronics and piezophototronics. Mater Today Nano, 2018, 4: 17–31
Duerloo KAN, Ong MT, Reed EJ. Intrinsic piezoelectricity in two-dimensional materials. J Phys Chem Lett, 2012, 3: 2871–2876
Wu W, Wang L, Li Y, et al. Piezoelectricity of single-atomic-layer MoS2 for energy conversion and piezotronics. Nature, 2014, 514: 470–474
Zhu H, Wang Y, Xiao J, et al. Observation of piezoelectricity in freestanding monolayer MoS2. Nat Nanotech, 2015, 10: 151–155
Dong L, Lou J, Shenoy VB. Large in-plane and vertical piezoelectricity in janus transition metal dichalchogenides. ACS Nano, 2017, 11: 8242–8248
Almaghbash ZAAR, Arbouche O, Dahani A, et al. Significant improvement in the piezoelectric properties and electromechanical coupling factors of wurtzite AlN compound under high pressures. J Comput Electron, 2021, 20: 2420–2430
Yang J, Wang A, Zhang S, et al. Coexistence of piezoelectricity and magnetism in two-dimensional vanadium dichalcogenides. Phys Chem Chem Phys, 2019, 21: 132–136
Guo SD, Zhu YT, Mu WQ, et al. A piezoelectric quantum spin Hall insulator with Rashba spin splitting in Janus monolayer SrAlGaSe4. J Mater Chem C, 2021, 9: 7465–7473
Guo SD, Mu WQ, Xiao XB, et al. Intrinsic room-temperature piezoelectric quantum anomalous hall insulator in Janus monolayer Fe2IX (X = Cl and Br). Nanoscale, 2021, 13: 12956–12965
Huang Y, Pan YH, Yang R, et al. Universal mechanical exfoliation of large-area 2D crystals. Nat Commun, 2020, 11: 2453
Liu Y, Li W, Li F, et al. Computational discovery of diverse functionalities in two-dimensional square disulfide monolayers: auxetic behavior, high curie temperature ferromagnets, electrocatalysts, and photocatalysts. J Mater Chem A, 2023, 11: 20254–20269
Kresse G, Joubert D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys Rev B, 1999, 59: 1758–1775
Kresse G, Furthmüller J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B, 1996, 54: 11169–11186
Perdew JP, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Phys Rev Lett, 1996, 77: 3865–3868
Liechtenstein AI, Anisimov VI, Zaanen J. Density-functional theory and strong interactions: Orbital ordering in Mott-Hubbard insulators. Phys Rev B, 1995, 52: R5467–R5470
Baroni S, de Gironcoli S, Dal Corso A, et al. Phonons and related crystal properties from density-functional perturbation theory. Rev Mod Phys, 2001, 73: 515–562
Heyd J, Scuseria GE, Ernzerhof M. Hybrid functionals based on a screened Coulomb potential. J Chem Phys, 2003, 118: 8207–8215
Neugebauer J, Scheffler M. Adsorbate-substrate and adsorbate-adsorbate interactions of Na and K adlayers on Al (111). Phys Rev B, 1992, 46: 16067–16080
Wang D, Wu R, Freeman AJ. First-principles theory of surface magnetocrystalline anisotropy and the diatomic-pair model. Phys Rev B, 1993, 47: 14932–14947
Evans RFL, Fan WJ, Chureemart P, et al. Atomistic spin model simulations of magnetic nanomaterials. J Phys-Condens Matter, 2014, 26: 103202
Wu X, Vanderbilt D, Hamann DR. Systematic treatment of displacements, strains, and electric fields in density-functional perturbation theory. Phys Rev B, 2005, 72: 035105
Mostofi AA, Yates JR, Lee YS, et al. Wannier90: A tool for obtaining maximally-localised Wannier functions. Comput Phys Commun, 2008, 178: 685–699
Wu QS, Zhang SN, Song HF, et al. WannierTools: An open-source software package for novel topological materials. Comput Phys Commun, 2018, 224: 405–416
He J, Ding G, Zhong C, et al. Cr2TiC2-based double MXenes: Novel 2D bipolar antiferromagnetic semiconductor with gate-controllable spin orientation toward antiferromagnetic spintronics. Nanoscale, 2019, 11: 356–364
Wang G. Theoretical prediction of the intrinsic half-metallicity in surface-oxygen-passivated Cr2N MXene. J Phys Chem C, 2016, 120: 18850–18857
He J, Lyu P, Nachtigall P. New two-dimensional Mn-based MXenes with room-temperature ferromagnetism and half-metallicity. J Mater Chem C, 2016, 4: 11143–11149
Li SS, Hu SJ, Ji WX, et al. Emergence of ferrimagnetic half-metallicity in two-dimensional MXene Mo3N2F2. Appl Phys Lett, 2017, 111: 202405
Zhou B, Wang X, Mi W. Superior electronic structure of two-dimensional 3D transition metal dicarbides for applications in spintronics. J Mater Chem C, 2018, 6: 4290–4299
Qin Y, Sayyad M, Montblanch ARP, et al. Reaching the excitonic limit in 2D janus monolayers by in situ deterministic growth. Adv Mater, 2022, 34: 2106222
Zhang C, Nie Y, Sanvito S, et al. First-principles prediction of a room-temperature ferromagnetic Janus VSSe monolayer with piezoelectricity, ferroelasticity, and large valley polarization. Nano Lett, 2019, 19: 1366–1370
Wu Y, Liu Q, Shi P, et al. High temperature ferromagnetic metal: A Janus CrSSe monolayer. Phys Chem Chem Phys, 2023, 25: 9958–9964
Zhang W, Zhang J, He C, et al. Constructing Janus SnSSe and graphene heterostructures as promising anode materials for Li-ion batteries. Intl J Energy Res, 2022, 46: 267–277
Lu AY, Zhu H, Xiao J, et al. Janus monolayers of transition metal dichalcogenides. Nat Nanotech, 2017, 12: 744–749
Molina-Sánchez A, Wirtz L. Phonons in single-layer and few-layer MoS2 and WS2. Phys Rev B, 2011, 84: 155413
Qin G, Yan QB, Qin Z, et al. Anisotropic intrinsic lattice thermal conductivity of phosphorene from first principles. Phys Chem Chem Phys, 2015, 17: 4854–4858
Wang J, Yip S, Phillpot SR, et al. Crystal instabilities at finite strain. Phys Rev Lett, 1993, 71: 4182–4185
Cadelano E, Colombo L. Effect of hydrogen coverage on the Young’s modulus of graphene. Phys Rev B, 2012, 85: 245434
Peng Q, De S. Outstanding mechanical properties of monolayer MoS2 and its application in elastic energy storage. Phys Chem Chem Phys, 2013, 15: 19427–19437
Lakes RS, Elms K. Indentability of conventional and negative Poisson’s ratio foams. J Composite Mater, 1993, 27: 1193–1202
Choi JB, Lakes RS. Fracture toughness of re-entrant foam materials with a negative Poisson’s ratio: Experiment and analysis. Int J Fract, 1996, 80: 73–83
Evans KE, Alderson A. Auxetic materials: Functional materials and structures from lateral thinking. Adv Mater, 2000, 12: 617–628
Jiang JW, Park HS. Negative Poisson’s ratio in single-layer black phosphorus. Nat Commun, 2014, 5: 4727
Zhong H, Huang K, Yu G, et al. Electronic and mechanical properties of few-layer borophene. Phys Rev B, 2018, 98: 054104
Yu L, Wang Y, Zheng X, et al. Emerging negative Poisson’s ratio driven by strong intralayer interaction response in rectangular transition metal chalcogenides. Appl Surf Sci, 2023, 610: 155478
Shi W, Wang Z. Mechanical and electronic properties of Janus monolayer transition metal dichalcogenides. J Phys-Condens Matter, 2018, 30: 215301
Moulkhalwa H, Zaoui Y, Obodo KO, et al. Half-metallic and half-semiconductor gaps in Cr-based chalcogenides: DFT+U calculations. J Supercond Nov Magn, 2019, 32: 635–649
Wang L, Liu J, Wang H, et al. Forming electron traps deactivates self-assembled crystalline organic nanosheets toward photocatalytic overall water splitting. Sci Bull, 2021, 66: 265–274
Wan Y, Wang L, Xu H, et al. A simple molecular design strategy for two-dimensional covalent organic framework capable of visible-light-driven water splitting. J Am Chem Soc, 2020, 142: 4508–4516
Zhao P, Ma Y, Lv X, et al. Two-dimensional III2-VI3 materials: Promising photocatalysts for overall water splitting under infrared light spectrum. Nano Energy, 2018, 51: 533–538
Gao X, Shen Y, Liu J, et al. Boosting the photon absorption, exciton dissociation, and photocatalytic hydrogen- and oxygen-evolution reactions by built-in electric fields in Janus platinum dichalcogenides. J Mater Chem C, 2021, 9: 15026–15033
Saha S, Sinha TP. Electronic structure, chemical bonding, and optical properties of paraelectric BaTiO3. Phys Rev B, 2000, 62: 8828–8834
Liu TY, Zhang QR, Zhuang SL. First principle studies on the electronic structures and absorption spectra under polarized light for the PbWO4 crystal with oxygen vacancy. Phys Lett A, 2004, 333: 473–477
Ju L, Bie M, Tang X, et al. Janus WSSe monolayer: An excellent photocatalyst for overall water splitting. ACS Appl Mater Interfaces, 2020, 12: 29335–29343
Ma X, Lv Y, Xu J, et al. A strategy of enhancing the photoactivity of g-C3N4 via doping of nonmetal elements: A first-principles study. J Phys Chem C, 2012, 116: 23485–23493
Nørskov JK, Rossmeisl J, Logadottir A, et al. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J Phys Chem B, 2004, 108: 17886–17892
German E, Gebauer R. Why are MoS2 monolayers not a good catalyst for the oxygen evolution reaction? Appl Surf Sci, 2020, 528: 146591
Qiao W, Xu W, Xu X, et al. Construction of active orbital via singleatom cobalt anchoring on the surface of 1T-MoS2 basal plane toward efficient hydrogen evolution. ACS Appl Energy Mater, 2020, 3: 2315–2322
Bardeen J, Shockley W. Deformation potentials and mobilities in nonpolar crystals. Phys Rev, 1950, 80: 72–80
Jiang S, Nazir S, Yang K. Origin of the large interfacial perpendicular magnetic anisotropy in MgO/Co2FeAl. Phys Rev B, 2020, 101: 134405
Wu Q, Zhang Y, Zhou Q, et al. Transition-metal dihydride monolayers: A new family oftwo-dimensional ferromagnetic materials with intrinsic room-temperature half-metallicity. J Phys Chem Lett, 2018, 9: 4260–4266
Webster L, Yan JA. Strain-tunable magnetic anisotropy in monolayer CrCl3, CrBr3, and CrI3. Phys Rev B, 2018, 98: 144411
Acknowledgements
This work was supported by the National Natural Science Foundation of China (11964024 and 12364038), the “Grassland Talents” Project of Inner Mongolia Autonomous Region (12000-12102613), and the Young Science and Technology Talents Cultivation Project of Inner Mongolia University (21200-5223708). The computational support from the PARATEAR at Guangzhou Supercomputer Center was acknowledged.
Author information
Authors and Affiliations
Contributions
Author contributions The initial idea was developed by Li F, Liu Y and Wang S performed the calculations under Li F’s supervision. All authors participated in the data analysis and writing and reading of the paper. Li F managed the project.
Corresponding author
Ethics declarations
Conflict of interest The authors declare that they have no conflict of interest.
Additional information
Supplementary information Experimental details and supporting data are available in the online version of the paper.
Yu Liu started his Master’s degree at Inner Mongolia University in 2020. After that, he continued his education as a PhD candidate under the supervision of Prof. Fengyu Li. His research focuses on theoretical design and physical property exploration of novel two-dimensional materials based on first-principles calculations.
Fengyu Li received her PhD degree from Dalian University of Technology (2012) and University of Puerto Rico (2014). After spending two years at University of Puerto Rico as a postdoc researcher, she served as a professor at Inner Mongolia University. Her research mainly focuses on low-dimensional materials design and simulation from first-principles and machine learning.
Supplementary Information
40843_2023_2708_MOESM1_ESM.pdf
A new 2D Janus family with multiple properties: auxetic behavior, straintunable photocatalyst, high Curie temperature ferromagnets, and piezoelectric quantum anomalous Hall insulator
Rights and permissions
About this article
Cite this article
Liu, Y., Wang, S. & Li, F. A new 2D Janus family with multiple properties: auxetic behavior, straintunable photocatalyst, high Curie temperature ferromagnets, and piezoelectric quantum anomalous Hall insulator. Sci. China Mater. 67, 1160–1172 (2024). https://doi.org/10.1007/s40843-023-2708-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s40843-023-2708-4