Monolayered semiconducting GeAsSe and SnSbTe with ultrahigh hole mobility

Abstract

High carrier mobility and a direct semiconducting band gap are two key properties of materials for electronic device applications. Using first-principles calculations, we predict two types of two-dimensional semiconductors, ultrathin GeAsSe and SnSbTe nanosheets, with desirable electronic and optical properties. Both GeAsSe and SnSbTe sheets are energetically favorable, with formation energies of −0.19 and −0.09 eV/atom, respectively, and have excellent dynamical and thermal stability, as determined by phonon dispersion calculations and Born–Oppenheimer molecular dynamics simulations. The relatively weak interlayer binding energies suggest that these monolayer sheets can be easily exfoliated from the bulk crystals. Importantly, monolayer GeAsSe and SnSbTe possess direct band gaps (2.56 and 1.96 eV, respectively) and superior hole mobility (~20 000 cm²·V⁻¹·s⁻¹), and both exhibit notable absorption in the visible region. A comparison of the band edge positions with the redox potentials of water reveals that layered GeAsSe and SnSbTe are potential photocatalysts for water splitting. These exceptional properties make layered GeAsSe and SnSbTe promising candidates for use in future high-speed electronic and optoelectronic devices.

Keywords

2D GeAsSe and SnSbTe / carrier mobility / photocatalysts / DFT calculations

References

[1] K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, M. I. Katsnelson, I. V. Grigorieva, S. V. Dubonos, and A. A. Firsov, Two-dimensional gas of massless Dirac fermions in graphene, Nature 438(7065), 197 (2005)

[2] J. Zhao, H. Liu, Z. Yu, R. Quhe, S. Zhou, Y. Wang, C. C. Liu, H. Zhong, N. Han, J. Lu, Y. Yao, and K. Wu, Rise of silicene: A competitive 2D material, Prog. Mater. Sci. 83, 24 (2016)

[3] Q. H. Wang, K. Kalantar-Zadeh, A. Kis, J. N. Coleman, and M. S. Strano, Electronics and optoelectronics of two-dimensional transition metal dichalcogenides, Nat. Nanotechnol. 7(11), 699 (2012)

[4] L. Li, Y. Yu, G. J. Ye, Q. Ge, X. Ou, H. Wu, D. Feng, X. H. Chen, and Y. Zhang, Black phosphorus field-effect transistors, Nat. Nanotechnol. 9(5), 372 (2014)

[5] Y. Pan, L. Zhang, L. Huang, L. Li, L. Meng, M. Gao, Q. Huan, X. Lin, Y. Wang, S. Du, H. J. Freund, and H. J. Gao, Construction of 2D atomic crystals on transition metal surfaces: Graphene, silicene, and hafnene, Small 10(11), 2215 (2014)

[6] J. Lu, A. Carvalho, X. K. Chan, H. Liu, B. Liu, E. S. Tok, K. P. Loh, A. H. Castro Neto, and C. H. Sow, Atomic healing of defects in transition metal dichalcogenides, Nano Lett. 15(5), 3524 (2015)

[7] M. S. Fuhrer, and J. Hone, Measurement of mobility in dual-gated MoS₂ transistors, Nat. Nanotechnol. 8(3), 146 (2013)

[8] H. Liu, A. T. Neal, Z. Zhu, Z. Luo, X. Xu, D. Tománek, and P. D. Ye, Phosphorene: An unexplored 2D semiconductor with a high hole mobility, ACS Nano 8(4), 4033 (2014)

[9] J. O. Island, G. A. Steele, H. S. J. v. d. Zant, and A. Castellanos-Gomez, Environmental instability of fewlayer black phosphorus, 2D Mater. 2(1), 011002 (2015)

[10] A. Ziletti, A. Carvalho, D. K. Campbell, D. F. Coker, and A. H. Castro Neto, Oxygen defects in phosphorene, Phys. Rev. Lett. 114(4), 046801 (2015)

[11] D. J. Late, B. Liu, H. S. S. R. Matte, C. N. R. Rao, and V. P. Dravid, Rapid characterization of ultrathin layers of chalcogenides on SiO₂/Si substrates, Adv. Funct. Mater. 22(9), 1894 (2012)

[12] S. L. Li, K. Tsukagoshi, E. Orgiu, and P. Samorì, Charge transport and mobility engineering in twodimensional transition metal chalcogenide semiconductors, Chem. Soc. Rev. 45(1), 118 (2016)

[13] R. Fei, W. Li, J. Li, and L. Yang, Giant piezoelectricity of monolayer group IV monochalcogenides: SnSe, SnS, GeSe, and GeS, Appl. Phys. Lett. 107(17), 173104 (2015)

[14] J. Zheng, H. Zhang, S. Dong, Y. Liu, C. Tai Nai, H. Suk Shin, H. Young Jeong, B. Liu, and K. Ping Loh, High yield exfoliation of two-dimensional chalcogenides using sodium naphthalenide, Nat. Commun. 5(1), 2995 (2014)

[15] Y. Guo, S. Zhou, Y. Bai, and J. Zhao, Enhanced piezoelectric effect in Janus group-III chalcogenide monolayers, Appl. Phys. Lett. 110(16), 163102 (2017)

[16] T. Gao, Q. Zhang, L. Li, X. Zhou, L. Li, H. Li, and T. Zhai, 2D ternary chalcogenides, Adv. Opt. Mater. 0(0), 1800058 (2018)

[17] Y. Guo, S. Zhou, Y. Bai, and J. Zhao, Oxidation resistance of monolayer group-IV monochalcogenides, ACS Appl. Mater. Interfaces 9(13), 12013 (2017)

[18] D. A. Bandurin, A. V. Tyurnina, G. L. Yu, A. Mishchenko, V. Zólyomi, S. V. Morozov, R. K. Kumar, R. V. Gorbachev, Z. R. Kudrynskyi, S. Pezzini, Z. D. Kovalyuk, U. Zeitler, K. S. Novoselov, A. Patanè, L. Eaves, I. V. Grigorieva, V. I. Fal’ko, A. K. Geim, and Y. Cao, High electron mobility, quantum Hall effect and anomalous optical response in atomically thin InSe, Nat. Nanotechnol. 12(3), 223 (2017)

[19] Y. Guo, S. Zhou, Y. Bai, and J. Zhao, Defects and oxidation of group-III monochalcogenide monolayers, J. Chem. Phys. 147(10), 104709 (2017)

[20] L. C. Gomes, A. Carvalho, and A. H. Castro Neto, Vacancies and oxidation of two-dimensional group-IV monochalcogenides, Phys. Rev. B 94(5), 054103 (2016)

[21] J. Wu, C. Tan, Z. Tan, Y. Liu, J. Yin, W. Dang, M. Wang, and H. Peng, Controlled synthesis of highmobility atomically thin bismuth oxyselenide crystals, Nano Lett. 17(5), 3021 (2017)

[22] B. Wang, X. Niu, Y. Ouyang, Q. Zhou, and J. Wang, Ultrathin semiconducting Bi₂Te₂S and Bi₂Te₂Se with high electron mobilities, J. Phys. Chem. Lett. 9(3), 487 (2018)

[23] J. Li, Z. Wang, Y. Wen, J. Chu, L. Yin, R. Cheng, L. Lei, P. He, C. Jiang, L. Feng, and J. He, Highperformance near-infrared photodetector based on ultrathin Bi₂O₂Se nanosheets, Adv. Funct. Mater. 28(10), 1706437 (2018)

[24] J. Wu, H. Yuan, M. Meng, C. Chen, Y. Sun, Z. Chen, W. Dang, C. Tan, Y. Liu, J. Yin, Y. Zhou, S. Huang, H. Q. Xu, Y. Cui, H. Y. Hwang, Z. Liu, Y. Chen, B. Yan, and H. Peng, High electron mobility and quantum oscillations in non-encapsulated ultrathin semiconducting Bi₂O₂Se, Nat. Nanotechnol. 12(6), 530 (2017)

[25] X. Zhang, X. Zhao, D. Wu, Y. Jing, and Z. Zhou, MnPSe₃ monolayer: A promising 2D visible-light photohydrolytic catalyst with high carrier mobility, Adv. Sci. 3(10), 1600062 (2016)

[26] X. Li, X. Wu, and J. Yang, Half-metallicity in MnPSe₃ exfoliated nanosheet with carrier doping,J. Am. Chem. Soc. 136(31), 11065 (2014)

[27] C. Zha, R. Wang, A. Smith, A. Prasad, R. A. Jarvis, and B. Luther-Davies, Optical properties and structural correlations of GeAsSe chalcogenide glasses, J. Mater. Sci. Mater. Electron. 18(S1), 389 (2007)

[28] D. T. Schaafsma, L. B. Shaw, B. Cole, J. S. Sanghera, and D. Aggarwal, Modeling of Dy³⁺-doped GeAsSe glass 1.3-m optical fiber amplifiers, IEEE Photonics Technol. Lett. 10(11), 1548 (1998)

[29] A. Zakery, and M. Hatami, Nonlinear optical properties of pulsed-laser-deposited GeAsSe films and simulation of a nonlinear directional coupler switch, J. Opt. Soc. Am. B 22(3), 591 (2005)

[30] N. Ashok, Y. L. Lee, and W. Shin, GeAsSe chalcogenide slot optical waveguide ring resonator for refractive index sensing, in: 2017 25th Optical Fiber Sensors Conference (OFS), 2017

[31] F. Hulliger and T. Siegrist, The crystal structure of Ge-AsSe, Mater. Res. Bull. 16(10), 1245 (1981)

[32] J. H. Yang, Y. Zhang, W. J. Yin, X. G. Gong, B. I. Yakobson, and S. H. Wei, Two-dimensional SiS layers with promising electronic and optoelectronic properties: Theoretical prediction, Nano Lett. 16(2), 1110 (2016)

[33] E. Ziambaras, J. Kleis, E. Schröder, and P. Hyldgaard, Potassium intercalation in graphite: A van der Waals density-functional study, Phys. Rev. B 76(15), 155425 (2007)

[34] R. Zacharia, H. Ulbricht, and T. Hertel, Interlayer cohesive energy of graphite from thermal desorption of polyaromatic hydrocarbons, Phys. Rev. B 69(15), 155406 (2004)

[35] 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)

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

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

[38] H. J. Monkhorst and J. D. Pack, Special points for Brillouin-zone integrations, Phys. Rev. B 13(12), 5188 (1976)

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

[40] S. Grimme, Semiempirical GGA-type density functional constructed with a long-range dispersion correction, J. Comput. Chem. 27(15), 1787 (2006)

[41] L. A. Burns, Á. V. Mayagoitia, B. G. Sumpter, and C. D. Sherrill, Density-functional approaches to noncovalent interactions: A comparison of dispersion corrections (DFT-D), exchange-hole dipole moment (XDM) theory, and specialized functionals, J. Chem. Phys. 134(8), 084107 (2011)

[42] 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)

[43] R. N. Barnett and U. Landman, Born-Oppenheimer molecular-dynamics simulations of finite systems: Structure and dynamics of (H₂O)₂, Phys. Rev. B 48(4), 2081 (1993)

[44] G. J. Martyna, M. L. Klein, and M. Tuckerman, Nosé–Hoover chains: The canonical ensemble via continuous dynamics, J. Chem. Phys. 97(4), 2635 (1992)

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

[46] L. Zhou, Y. Guo, and J. Zhao, GeAs and SiAs monolayers: Novel 2D semiconductors with suitable band structures, Physica E 95, 149 (2018)

[47] V. Chakrapani, J. C. Angus, A. B. Anderson, S. D. Wolter, B. R. Stoner, and G. U. Sumanasekera, Charge transfer equilibria between diamond and an aqueous oxygen electrochemical redox couple, Science 318(5855), 1424 (2007)

[48] H. L. Zhuang and R. G. Hennig, Single-layer group- III monochalcogenide photocatalysts for water splitting, Chem. Mater. 25(15), 3232 (2013)

[49] Z. Ma, J. Zhuang, X. Zhang, and Z. Zhou, SiP monolayers: New 2D structures of group IV–V compounds for visible-light photohydrolytic catalysts, Front. Phys. 13(3), 138104 (2018)

[50] X. Zhang, Z. Zhang, D. Wu, X. Zhang, X. Zhao, and Z. Zhou, Computational screening of 2D materials and rational design of heterojunctions for water splitting photocatalysts, Small Methods 2(5), 1700359 (2018)

[51] A. R. Beal and H. P. Hughes, Kramers-Kronig analysis of the reflectivity spectra of 2H-MoS₂, 2H-MoSe₂ and 2H-MoTe₂, J. Phys. C Solid State Phys. 12(5), 881 (1979)

[52] S. Takagi, A. Toriumi, M. Iwase, and H. Tango, On the universality of inversion layer mobility in Si MOSFET’s: Part I-effects of substrate impurity concentration, IEEE Trans. Electron Dev. 41(12), 2357 (1994)

[53] S. Bruzzone and G. Fiori, Ab-initio simulations of deformation potentials and electron mobility in chemically modified graphene and two-dimensional hexagonal boron-nitride, Appl. Phys. Lett. 99(22), 222108 (2011)

[54] G. Fiori and G. Iannaccone, Multiscale modeling for graphene-based nanoscale transistors, Proc. IEEE 101(7), 1653 (2013)

[55] J. Qiao, X. Kong, Z. X. Hu, F. Yang, and W. Ji, Highmobility transport anisotropy and linear dichroism in few-layer black phosphorus, Nat. Commun. 5(1), 4475 (2014)

[56] J. Dai and X. C. Zeng, Titanium trisulfide monolayer: Theoretical prediction of a new directg semiconductor with high and anisotropic carrier mobility, Angew. Chem. Int. Ed. 127(26), 7682 (2015)

[57] Y. Guo, S. Zhou, J. Zhang, Y. Bai, and J. Zhao, Atomic structures and electronic properties of phosphorene grain boundaries, 2D Mater. 3(2), 025008 (2016)

[58] W. Zhang, Y. G. Wang, Y. Ding, J. Yin, and P. Zhang, Two-dimensional GeAsSe with high and unidirectional conductivity, Nanoscale (2018)

RIGHTS & PERMISSIONS

2018 Higher Education Press and Springer-Verlag GmbH Germany, part of Springer Nature