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Two-dimensional (2D) ferroelectric materials are important materials for both fundamental properties and potential applications. Especially, group Ⅳ monochalcogenide possesses highest thermoelectric performance and intrinsic ferroelectric polarization properties and can sever as a model to explore ferroelectric polarization properties. However, due to the relatively large exfoliation energy, the creation of high-quality and large-size monolayer group Ⅳ monochalcogenide is not so easy, which seriously hinders the integration of these materials into the fast-developing field of 2D materials and their heterostructures. Herein, monolayer GeS is successfully fabricated on Cu(111) substrate by molecular beam epitaxy method, and the lattice structure and the electronic band structure of monolayer GeS are systematically characterized by high-resolution scanning tunneling microscopy, low-energy electron diffraction, in-situ X-ray photoelectron spectroscopy, Raman spectra, and angle-resolved photoelectron spectroscopy, and density functional theory calculations. All atomically resolved STM images reveal that the obtained monolayer GeS has an orthogonal lattice structure, which consists with theoretical prediction. Meanwhile, the distinct moiré pattern formed between monolayer GeS and Cu(111) substrate also confirms the orthogonal lattice structure. In order to examine the chemical composition and valence state of as-prepared monolayer GeS, in-situ XPS is utilized without being exposed to air. The measured spectra of XPS core levels suggest that the valence states of Ge and S elements are identified to be +2 and –2, respectively and the atomic ratio of Ge/S is 1∶1.5, which is extremely close to the stoichiometric ratio of 1∶1 for GeS. To further corroborate the quality and lattice structure of the monolayer GeS film, ex-situ Raman measurements are also performed for monolayer GeS on highly oriented pyrolytic graphene (HOPG) and multilayer graphene substrate. Three well-defined typical characteristic Raman peaks of GeS are observed. Finally, in-situ ARPES measurement are conducted to determine the electronic band structure of monolayer GeS on Cu(111). The results demonstrate that the monolayer GeS has a nearly flat band electronic band structure, consistent with our density functional theory calculation. The realization and investigation of the monolayer GeS extend the scope of 2D ferroelectric materials and make it possible to prepare high quality and large size monolayer group Ⅳ monochalcogenides, which is beneficial to the application of this main group material to the rapidly developing 2D ferroelectric materials and heterojunction research.
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Keywords:
- 2D ferroelectrics /
- transition metal monochalcogenides /
- germanium sulfide /
- scanning tunneling microscopy /
- X-ray photoemission spectroscopy
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[49] Ul Haq B, AlFaify S, Laref A 2019 J. Phys. Chem. C 123 18124Google Scholar
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Wang H, Xu M, Zheng R K 2020 Acta Phys. Sin. 69 017301Google Scholar
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图 1 单层GeS原子分辨STM测量 (a) MBE生长腔结构(左)与STM测量和单层GeS晶体结构(右); (b), (c) 单层GeS在Cu(111)衬底表面形成的摩尔条纹及其快速傅里叶变换, 图像大小为14 nm×14 nm; (d) Cu(111)上单层GeS生长顶示意图; (e), (f) 单层GeS原子分辨STM图像及其快速傅里叶变换, 样品偏压1.2 V和隧穿电流0.60 nA, 图像大小为14 nm×14 nm
Figure 1. Atomically resolved STM measurements of monolayer GeS: (a) Schematic of MBE growth chamber (left) and STM set-up and crystal structure of monolayer GeS (right); (b), (c) moiré pattern formed betweem monolayer GeS and Cu(111) substrate and its fast Fourier transform with the image size of 14 nm × 14 nm; (d) schematic of the monolayer GeS grown on Cu(111); (e), (f) atomically resolved STM images of monolayer GeS and its fast Fourier transform with sample bias voltage of 1.2 V and tunneling current of 0.60 nA, and image size of 14 nm × 14 nm.
图 3 Γ→Χ和Γ→Y高对称方向的能带结构 (a), (b) 单层GeS理论计算能带结构; (c), (d) Cu(111)衬底能带结构; (e), (f)单层GeS/Cu(111)异质结理论计算的能带结构(上)与APRES测量的能带结构(下)
Figure 3. Electronic band structures along Γ→Χ and Γ→Y high symmetry directions: (a), (b) Theoretically calculated electronic band structure of monolayer GeS; (c), (d) elelctronic band structure of Cu(111) substrate; (e), (f) theoretically calculated electronic band structure of monolayer GeS/Cu(111) heterojunction (top) and electronic band structure measured by APRES (bottom).
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[1] Khan A I, Keshavarzi A, Datta S 2020 Nat. Electron. 3 588Google Scholar
[2] Wang S, Liu L, Gan L, Chen H, Hou X, Ding Y, Ma S, Zhang D W, Zhou P 2021 Nat. Commun. 12 53Google Scholar
[3] John R A, Demirağ Y, Shynkarenko Y, Berezovska Y, Ohannessian N, Payvand M, Zeng P, Bodnarchuk M I, Krumeich F, Kara G, Shorubalko I, Nair M V, Cooke G A, Lippert T, Indiveri G, Kovalenko M V 2022 Nat. Commun. 13 2074Google Scholar
[4] Wang J, Wang F, Wang Z, Huang W, Yao Y, Wang Y, Yang J, Li N, Yin L, Cheng R, Zhan X, Shan C, He J 2021 Sci. Bull. 66 2288Google Scholar
[5] Junquera J, Ghosez P 2003 Nature 422 506Google Scholar
[6] Lee D, Lu H, Gu Y, Choi S Y, Li S D, Ryu S, Paudel T R, Song K, Mikheev E, Lee S, Stemmer S, Tenne D A, Oh S H, Tsymbal E Y, Wu X, Chen L Q, Gruverman A, Eom C B 2015 Science 349 1314Google Scholar
[7] 胡婷, 阚二军 2018 物理学报 67 157701Google Scholar
Hu T, Kan E J 2018 Acta Phys. Sin. 67 157701Google Scholar
[8] Yang Q, Xiong W, Zhu L, Gao G, Wu M 2017 J. Am. Chem. Soc. 139 11506Google Scholar
[9] Wu M, Dong S, Yao K, Liu J, Zeng X C 2016 Nano Lett. 16 7309Google Scholar
[10] Voiry D, Goswami A, Kappera R, et al. 2015 Nat. Chem. 7 45Google Scholar
[11] Chang K, Liu J, Lin H, Wang N, Zhao K, Zhang A, Jin F, Zhong Y, Hu X, Duan W, Zhang Q, Fu L, Xue Q K, Chen X, Ji S H 2016 Science 353 274Google Scholar
[12] Liu F, You L, Seyler K L, Li X, Yu P, Lin J, Wang X, Zhou J, Wang H, He H, Pantelides S T, Zhou W, Sharma P, Xu X, Ajayan P M, Wang J, Liu Z 2016 Nat. Commun. 7 12357Google Scholar
[13] Ding W, Zhu J, Wang Z, Gao Y, Xiao D, Gu Y, Zhang Z, Zhu W 2017 Nat. Commun. 8 14956Google Scholar
[14] Bao Y, Song P, Liu Y, Chen Z, Zhu M, Abdelwahab I, Su J, Fu W, Chi X, Yu W, Liu W, Zhao X, Xu Q H, Yang M, Loh K P 2019 Nano Lett. 19 5109Google Scholar
[15] Sui F, Jin M, Zhang Y, Qi R, Wu Y N, Huang R, Yue F, Chu J 2023 Nat. Commun. 14 36Google Scholar
[16] Yang Q, Wu M, Li J 2018 J. Phys. Chem. Lett. 9 7160Google Scholar
[17] Meng P, Wu Y, Bian R, Pan E, Dong B, Zhao X, Chen J, Wu L, Sun Y, Fu Q, Liu Q, Shi D, Zhang Q, Zhang Y W, Liu Z, Liu F 2022 Nat. Commun. 13 7696Google Scholar
[18] 孟雨欣, 赵漪凡, 李绍春 2021 物理学报 70 148101Google Scholar
Meng Y X, Zhao Y F, Li S C 2021 Acta Phys. Sin. 70 148101Google Scholar
[19] 叶倩, 沈阳, 袁野, 赵祎峰, 段纯刚 2020 物理学报 69 217710Google Scholar
Ye Q, Shen Y, Yuan Y, Zhao Y F, Duan C G 2020 Acta Phys. Sin. 69 217710Google Scholar
[20] Chowdhury T, Taneja C, Vasdev A, Ghosh P, Sheet G, Kumar G V P, Rahman A 2022 Adv. Electron. Mater. 8 2101158Google Scholar
[21] Sutter E, Zhang B, Sun M, Sutter P 2019 ACS Nano 13 9352Google Scholar
[22] Guan Z, Zhao Y, Wang X, Zhong N, Deng X, Zheng Y, Wang J, Xu D, Ma R, Yue F, Cheng Y, Huang R, Xiang P, Wei Z, Chu J, Duan C 2022 ACS Nano 16 1308Google Scholar
[23] Yu H, Gao D, Wang X, Du X, Lin X, Guo W, Zou R, Jin C, Li K, Chen Y 2018 NPG Asia Mater. 10 882Google Scholar
[24] Zhu M, Zhong M, Guo X, Wang Y, Chen Z, Huang H, He J, Su C, Loh K P 2021 Adv. Opt. Mater. 9 2101200Google Scholar
[25] Sutter P, Komsa H P, Lu H, Gruverman A, Sutter E 2021 Nano Today 37 101082Google Scholar
[26] Du R, Wang Y, Cheng M, Wang P, Li H, Feng W, Song L, Shi J, He J 2022 Nat. Commun. 13 6130Google Scholar
[27] Higashitarumizu N, Kawamoto H, Lee C J, Lin B H, Chu F H, Yonemori I, Nishimura T, Wakabayashi K, Chang W H, Nagashio K 2020 Nat. Commun. 11 2428Google Scholar
[28] Khan H, Mahmood N, Zavabeti A, Elbourne A, Rahman Md A, Zhang B Y, Krishnamurthi V, Atkin P, Ghasemian M B, Yang J, Zheng G, Ravindran A R, Walia S, Wang L, Russo S P, Daeneke T, Li Y, Kalantar-Zadeh K 2020 Nat. Commun. 11 3449Google Scholar
[29] Chang K, Küster F, Miller B J, Ji J R, Zhang J L, Sessi P, Barraza-Lopez S, Parkin S S P 2020 Nano Lett. 20 6590Google Scholar
[30] Chiu M H, Ji X, Zhang T, Mao N, Luo Y, Shi C, Zheng X, Liu H, Han Y, Wilson W L, Luo Z, Tung V, Kong J 2023 Adv. Electron. Mater. 9 2201031Google Scholar
[31] Sarkar A S, Konidakis I, Gagaoudakis E, Maragkakis G M, Psilodimitrakopoulos S, Katerinopoulou D, Sygellou L, Deligeorgis G, Binas V, Oikonomou I M, Komninou P, Kiriakidis G, Kioseoglou G, Stratakis E 2023 Adv. Sci. 10 2201842Google Scholar
[32] Zhou B, Gong S J, Jiang K, Xu L, Shang L, Zhang J, Hu Z, Chu J 2020 J. Mater. Chem. C 8 89Google Scholar
[33] Yan Y, Deng Q, Li S, Guo T, Li X, Jiang Y, Song X, Huang W, Yang J, Xia C 2021 Nanoscale 13 16122Google Scholar
[34] Pan J, Jing S, Chen W, Bian B, Liao B, Wan G 2022 Appl. Phys. A 128 141Google Scholar
[35] Sharma D, Kumar R, Pal A, Sakhuja N, Bhat N 2023 ACS Appl. Electron. Mater. 5 3162Google Scholar
[36] Xia F, Wang H, Hwang J C M, Neto A H C, Yang L 2019 Nat. Rev. Phys. 1 306Google Scholar
[37] Wu S, Chen Y, Wang X, Jiao H, Zhao Q, Huang X, Tai X, Zhou Y, Chen H, Wang X, Huang S, Yan H, Lin T, Shen H, Hu W, Meng X, Chu J, Wang J 2022 Nat. Commun. 13 3198Google Scholar
[38] Guan S, Liu C, Lu Y, Yao Y, Yang S A 2018 Phys. Rev. B 97 144104Google Scholar
[39] Xu Y, Zhang H, Shao H, Ni G, Li J, Lu H, Zhang R, Peng B, Zhu Y, Zhu H 2017 Phys. Rev. B 96 245421Google Scholar
[40] Li Z, Gu Y, He C, Zou X 2022 Phys. Rev. B 106 035426Google Scholar
[41] Von Rohr F O, Ji H, Cevallos F A, Gao T, Ong N P, Cava R J 2017 J. Am. Chem. Soc. 139 2771Google Scholar
[42] Luo N, Wang C, Jiang Z, Xu Y, Zou X, Duan W 2018 Adv. Funct. Mater. 28 1804581Google Scholar
[43] Nguyen L T, Makov G 2022 Cryst. Growth Des. 22 4956Google Scholar
[44] Zhang S, Xie M, Li F, Yan Z, Li Y, Kan E, Liu W, Chen Z, Zeng H 2016 Angew. Chem. Int. Ed. 128 1698Google Scholar
[45] Jia S, Li H, Gotoh T, Longeaud C, Zhang B, Lü J, Lü S, Zhu M, Song Z, Liu Q, Robertson J, Liu M 2020 Nat. Commun. 11 4636Google Scholar
[46] Feng M, Liu S C, Hu L, Wu J, Liu X, Xue D J, Hu J S, Wan L J 2021 J. Am. Chem. Soc. 143 9664Google Scholar
[47] Chen H, Keiser C, Du S, Gao H J, Sutter P, Sutter E 2017 Phys. Chem. Chem. Phys. 19 32473Google Scholar
[48] Ribeiro H B, Ramos S, Seixas L, De Matos C J S, Pimenta M A 2019 Phys. Rev. B 100 094301Google Scholar
[49] Ul Haq B, AlFaify S, Laref A 2019 J. Phys. Chem. C 123 18124Google Scholar
[50] Zhou Y, Wu D, Zhu Y, Cho Y, He Q, Yang X, Herrera K, Chu Z, Han Y, Downer M C, Peng H, Lai K 2017 Nano Lett. 17 5508Google Scholar
[51] 王慧, 徐萌, 郑仁奎 2020 物理学报 69 017301Google Scholar
Wang H, Xu M, Zheng R K 2020 Acta Phys. Sin. 69 017301Google Scholar
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