Interfacial properties of 2D WS₂ on SiO₂ substrate from X-ray photoelectron spectroscopy and first-principles calculations

Abstract

Two-dimensional (2D) WS₂ films were deposited on SiO₂ wafers, and the related interfacial properties were investigated by high-resolution X-ray photoelectron spectroscopy (XPS) and first-principles calculations. Using the direct (indirect) method, the valence band offset (VBO) at monolayer WS₂/SiO₂ interface was found to be 3.97 eV (3.86 eV), and the conduction band offset (CBO) was 2.70 eV (2.81 eV). Furthermore, the VBO (CBO) at bulk WS₂/SiO₂ interface is found to be about 0.48 eV (0.33 eV) larger due to the interlayer orbital coupling and splitting of valence and conduction band edges. Therefore, the WS₂/SiO₂ heterostructure has a Type I energy-band alignment. The band offsets obtained experimentally and theoretically are consistent except the narrower theoretical bandgap of SiO₂. The theoretical calculations further reveal a binding energy of 75 meV per S atom and the totally separated partial density of states, indicating a weak interaction and negligible Fermi level pinning effect between WS₂ monolayer and SiO₂ surface. Our combined experimental and theoretical results provide proof of the sufficient VBOs and CBOs and weak interaction in 2D WS₂/SiO₂ heterostructures.

Graphical abstract

Keywords

band offsets / WS₂ / SiO₂ / X-ray photoelectron spectroscopy / first-principles calculations

References

[1] K. F. Mak , C. Lee , J. Hone , J. Shan , T. F. Heinz . Atomically thin MoS₂: A new direct-gap semiconductor. Phys. Rev. Lett., 2010, 105( 13): 136805

[2] G. Eda , H. Yamaguchi , D. Voiry , T. Fujita , M. W. Chen , M. Chhowalla . Photoluminescence from chemically exfoliated MoS₂. Nano Lett., 2011, 11( 12): 5111

[3] J. N. Coleman , M. Lotya , A. O’Neill , S. D. Bergin , P. J. King , U. Khan , K. Young , A. Gaucher , S. De , R. J. Smith , I. V. Shvets , S. K. Arora , G. Stanton , H. Y. Kim , K. Lee , G. T. Kim , G. S. Duesberg , T. Hallam , J. J. Boland , J. J. Wang , J. F. Donegan , J. C. Grunlan , G. Moriarty , A. Shmeliov , R. J. Nicholls , J. M. Perkins , E. M. Grieveson , K. Theuwissen , D. W. McComb , P. D. Nellist , V. Nicolosi . Two-dimensional nanosheets produced by liquid exfoliation of layered materials. Science, 2011, 331( 6017): 568

[4] Y. J. Zhan , Z. Liu , S. Najmaei , P. M. Ajayan , J. Lou . Large-area vapor-phase growth and characterization of MoS₂ atomic layers on a SiO₂ substrate. Small, 2012, 8( 7): 966

[5] Y. H. Lee , X. Q. Zhang , W. J. Zhang , M. T. Chang , C. T. Lin , K. D. Chang , Y. C. Yu , J. T. W. Wang , C. S. Chang , L. J. Li , T. W. Lin . Synthesis of large-area MoS₂ atomic layers with chemical vapor deposition. Adv. Mater., 2012, 24( 17): 2320

[6] P. Y. Liu , T. Luo , J. Xing , H. Xu , H. Y. Hao , H. Liu , J. J. Dong . Large-area WS₂ film with big single domains grown by chemical vapor deposition. Nanoscale Res. Lett., 2017, 12( 1): 558

[7] A. L. Elías , N. Perea-Lopez , A. Castro-Beltran , A. Berkdemir , R. T. Lv , S. M. Feng , A. D. Long , T. Hayashi , Y. A. Kim , M. Endo , H. R. Gutierrez , N. R. Pradhan , L. Balicas , T. E. Mallouk , F. Lopez-Urias , H. Terrones , M. Terrones . Controlled synthesis and transfer of large-area WS₂ sheets: From single layer to few layers. ACS Nano, 2013, 7( 6): 5235

[8] H. L. Zhu , C. J. Zhou , B. S. Tang , W. F. Yang , J. W. Chai , W. L. Tay , H. Gong , J. S. Pan , W. D. Zou , S. J. Wang , D. Z. Chi . Band alignment of 2D WS₂/HfO₂ interfaces from X-ray photoelectron spectroscopy and first-principles calculations. Appl. Phys. Lett., 2018, 112( 17): 171604

[9] M. X. Ye , D. Y. Zhang , Y. K. Yap . Recent advances in electronic and optoelectronic devices based on two-dimensional transition metal dichalcogenides. Electronics (Basel), 2017, 6( 2): 43

[10] C. X. Cong , J. Z. Shang , Y. L. Wang , T. Yu . Optical properties of 2D semiconductor WS₂. Adv. Opt. Mater., 2018, 6( 1): 1700767

[11] P. J. Schuck , W. Bao , N. J. Borys . A polarizing situation: Taking an in-plane perspective for next-generation near-field studies. Front. Phys., 2016, 11( 2): 117804

[12] Z. C. Zhou , F. Y. Yang , S. Wang , L. Wang , X. F. Wang , C. Wang , Y. Xie , Q. Liu . Emerging of two-dimensional materials in novel memristor. Front. Phys., 2022, 17( 2): 23204

[13] H. L. Zhu , W. H. Yang , Y. P. Wu , W. Lin , J. Y. Kang , C. J. Zhou . Au and Ti induced charge redistributions on monolayer WS₂. Chin. Phys. B, 2015, 24( 7): 077301

[14] T. LaMountain , E. J. Lenferink , Y. J. Chen , T. K. Stanev , N. P. Stern . Environmental engineering of transition metal dichalcogenide optoelectronics. Front. Phys., 2018, 13( 4): 138114

[15] G. Luo , Z. Z. Zhang , H. O. Li , X. X. Song , G. W. Deng , G. Cao , M. Xiao , G. P. Guo . Quantum dot behavior in transition metal dichalcogenides nanostructures. Front. Phys., 2017, 12( 4): 128502

[16] H. M. Hill , A. F. Rigosi , K. T. Rim , G. W. Flynn , T. F. Heinz . Band alignment in MoS₂/WS₂ transition metal dichalcogenide heterostructures probed by scanning tunneling microscopy and spectroscopy. Nano Lett., 2016, 16( 8): 4831

[17] Y. Z. Guo , J. Robertson . Band engineering in transition metal dichalcogenides: Stacked versus lateral heterostructures. Appl. Phys. Lett., 2016, 108( 23): 233104

[18] J. Jadczak , J. Kutrowska-Girzycka , P. Kapuscinski , Y. S. Huang , A. Wojs , L. Bryja . Probing of free and localized excitons and trions in atomically thin WSe₂, WS₂, MoSe₂ and MoS₂ in photoluminescence and reflectivity experiments. Nanotechnology, 2017, 28( 39): 395702

[19] P. K. Nayak , F. C. Lin , C. H. Yeh , J. S. Huang , P. W. Chiu . Robust room temperature valley polarization in monolayer and bilayer WS₂. Nanoscale, 2016, 8( 11): 6035

[20] N. Ubrig , S. Jo , M. Philippi , D. Costanzo , H. Berger , A. B. Kuzmenko , A. F. Morpurgo . Microscopic origin of the valley Hall effect in transition metal dichalcogenides revealed by wavelength-dependent mapping. Nano Lett., 2017, 17( 9): 5719

[21] M. Van der Donck , M. Zarenia , F. M. Peeters . Strong valley Zeeman effect of dark excitons in monolayer transition metal dichalcogenides in a tilted magnetic field. Phys. Rev. B, 2018, 97( 8): 081109

[22] M. W. Iqbal , M. Z. Iqbal , M. F. Khan , M. A. Kamran , A. Majid , T. Alharbi , J. Eom . Tailoring the electrical and photo-electrical properties of a WS₂ field effect transistor by selective n-type chemical doping. RSC Advances, 2016, 6( 29): 24675

[23] N. J. Huo , S. X. Yang , Z. M. Wei , S. S. Li , J. B. Xia , J. B. Li . Photoresponsive and gas sensing field-effect transistors based on multilayer WS₂ nanoflakes. Sci. Rep., 2014, 4( 1): 5209

[24] D. Akinwande , N. Petrone , J. Hone . Two-dimensional flexible nanoelectronics. Nat. Commun., 2014, 5( 1): 5678

[25] Y. Wang , D. Kong , S. Huang , Y. Shi , M. Ding , Y. Von Lim , T. Xu , F. Chen , X. Li , H. Y. Yang . 3D carbon foam-supported WS₂ nanosheets for cable-shaped flexible sodium ion batteries. J. Mater. Chem., 2018, 6( 23): 10813

[26] C. Y. Lan , Z. Y. Zhou , Z. F. Zhou , C. Li , L. Shu , L. F. Shen , D. P. Li , R. T. Dong , S. P. Yip , J. Ho . Wafer-scale synthesis of monolayer WS₂ for high-performance flexible photodetectors by enhanced chemical vapor deposition. Nano Res., 2018, 11( 6): 3371

[27] C. Ouyang , Y. X. Chen , Z. Y. Qin , D. W. Zeng , J. Zhang , H. Wang , C. S. Xie . Two-dimensional WS₂-based nanosheets modified by Pt quantum dots for enhanced room-temperature NH₃ sensing properties. Appl. Surf. Sci., 2018, 455 : 45

[28] G. A. Asres , J. J. Baldoví , A. Dombovari , T. Järvinen , G. S. Lorite , M. Mohl , A. Shchukarev , A. Pérez Paz , L. Xian , J. P. Mikkola , A. L. Spetz , H. Jantunen , Á. Rubio , K. Kordás . Ultrasensitive H₂S gas sensors based on p-type WS₂ hybrid materials. Nano Res., 2018, 11( 8): 4215

[29] Q. H. Xu , Y. T. Lu , S. Y. Zhao , N. Hu , Y. W. Jiang , H. Li , Y. Wang , H. Q. Gao , Y. Li , M. Yuan , L. Chu , J. H. Li , Y. N. Xie . A wind vector detecting system based on triboelectric and photoelectric sensors for simultaneously monitoring wind speed and direction. Nano Energy, 2021, 89 : 106382

[30] Q. H. Xu , Y. S. Fang , B. Q. S. Jing , N. Hu , K. Lin , Y. F. Pan , L. Xu , H. Q. Gao , M. Yuan , L. Chu , Y. W. Ma , Y. N. Xie , J. Chen , L. H. Wang . A portable triboelectric spirometer for wireless pulmonary function monitoring. Biosens. Bioelectron., 2021, 187 : 113329

[31] Z. Z. Yan , Z. H. Jiang , J. P. Lu , Z. H. Ni . Interfacial charge transfer in WS₂ monolayer/CsPbBr₃ microplate heterostructure. Front. Phys., 2018, 13( 4): 138115

[32] W. J. Yin , X. L. Zeng , B. Wen , Q. X. Ge , Y. Xu , G. Teobaldi , L. M. Liu . The unique carrier mobility of Janus MoSSe/GaN heterostructures. Front. Phys., 2021, 16( 3): 33501

[33] H. Wang , D. L. Ren , C. Lu , X. B. Yan . Investigation of multilayer WS₂ flakes as charge trapping stack layers in non-volatile memories. Appl. Phys. Lett., 2018, 112( 23): 231903

[34] O. Zheliuk , J. M. Lu , J. Yang , J. T. Ye . Monolayer superconductivity in WS₂. Phys. Status Solidi Rapid Res. Lett., 2017, 11( 9): 1700245

[35] S. Ulstrup , R. J. Koch , D. Schwarz , K. M. McCreary , B. T. Jonker , S. Singh , A. Bostwick , E. Rotenberg , C. Jozwiak , J. Katoch . Imaging microscopic electronic contrasts at the interface of single-layer WS₂ with oxide and boron nitride substrates. Appl. Phys. Lett., 2019, 114( 15): 151601

[36] W. F. Yang , H. Kawai , M. Bosman , B. S. Tang , J. W. Chai , W. L. Tay , J. Yang , H. L. Seng , H. L. Zhu , H. Gong , H. F. Liu , K. E. J. Goh , S. J. Wang , D. Z. Chi . Interlayer interactions in 2D WS₂/MoS₂ heterostructures monolithically grown by in situ physical vapor deposition. Nanoscale, 2018, 10( 48): 22927

[37] B. S. Tang , Z. G. Yu , L. Huang , J. W. Chai , S. L. Wong , J. Deng , W. F. Yang , H. Gong , S. J. Wang , K. W. Ang , Y. W. Zhang , D. Z. Chi . Direct n- to p-type channel conversion in monolayer/few-layer WS₂ field-effect transistors by atomic nitrogen treatment. ACS Nano, 2018, 12( 3): 2506

[38] H. R. Gutiérrez , N. Perea-Lopez , A. L. Elias , A. Berkdemir , B. Wang , R. Lv , F. Lopez-Urias , V. H. Crespi , H. Terrones , M. Terrones . Extraordinary room-temperature photoluminescence in triangular WS₂ monolayers. Nano Lett., 2013, 13( 8): 3447

[39] L. Yang , X. B. Zhu , S. J. Xiong , X. L. Wu , Y. Shan , P. K. Chu . Synergistic WO₂·2H₂O nanoplates/WS₂ hybrid catalysts for high-efficiency hydrogen evolution. ACS Appl. Mater. Interfaces, 2016, 8( 22): 13966

[40] R. Bhandavat , L. David , G. Singh . Synthesis of surface-functionalized WS₂ nanosheets and performance as Li-ion battery anodes. J. Phys. Chem. Lett., 2012, 3( 11): 1523

[41] S. Cadot , O. Renault , D. Rouchon , D. Mariolle , E. Nolot , C. Thieuleux , L. Veyre , H. Okuno , F. Martin , E. A. Quadrelli . Low-temperature and scalable CVD route to WS₂ monolayers on SiO₂/Si substrates. J. Vac. Sci. Technol. A, 2017, 35( 6): 061502

[42] E. A. Kraut , R. W. Grant , J. R. Waldrop , S. P. Kowalczyk . Precise determination of the valence-band edge in X-ray photoemission spectra-application to measurement of semi-conductor interface potentials. Phys. Rev. Lett., 1980, 44( 24): 1620

[43] J. G. Tao , J. W. Chai , Z. Zhang , J. S. Pan , S. J. Wang . The energy-band alignment at molybdenum disulphide and high-k dielectrics interfaces. Appl. Phys. Lett., 2014, 104( 23): 232110

[44] A. Santoni , F. Biccari , C. Malerba , M. Valentini , R. Chierchia , A. Mittiga . Valence band offset at the CdS/Cu₂ZnSnS₄ interface probed by X-ray photoelectron spectroscopy. J. Phys. D Appl. Phys., 2013, 46( 17): 175101

[45] F. J. Grunthaner , B. F. Lewis , N. Zamini , J. Maserjian , A. Madhukar . XPS studies of structure-induced radiation effects at the Si/SiO₂ interface. IEEE Trans. Nucl. Sci., 1980, 27( 6): 1640

[46] J. Zhang , S. H. Wei , X. L. Wang , J. J. Xiang , W. W. Wang . Experimental estimation of charge neutrality level of SiO₂. Appl. Surf. Sci., 2017, 422 : 690

[47] H. L. Zhu , C. J. Zhou , X. J. Huang , X. L. Wang , H. Z. Xu , Y. Lin , W. H. Yang , Y. P. Wu , W. Lin , F. Guo . Evolution of band structures in MoS₂-based homo- and heterobilayers. J. Phys. D Appl. Phys., 2016, 49( 6): 065304

[48] Y. K. Lin , R. S. Chen , T. C. Chou , Y. H. Lee , Y. F. Chen , K. H. Chen , L. C. Chen . Thickness-dependent binding energy shift in few-layer MoS₂ grown by chemical vapor deposition. ACS Appl. Mater. Interfaces, 2016, 8( 34): 22637

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

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

[51] S. Grimme , J. Antony , S. Ehrlich , H. Krieg . A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys., 2010, 132( 15): 154104

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

[53] L. Bengtsson . Dipole correction for surface supercell calculations. Phys. Rev. B, 1999, 59( 19): 12301

[54] O. I. Malyi , V. V. Kulish , C. Persson . In search of new reconstructions of (001) alpha-quartz surface: A first principles study. RSC Advances, 2014, 4( 98): 55599

[55] W. L. Scopel , A. J. R. da Silva , A. Fazzio . Amorphous HfO₂ and Hf_1−xSi_xO via a melt-and-quench scheme using ab initio molecular dynamics. Phys. Rev. B, 2008, 77( 17): 172101

[56] W. L. Scopel , R. H. Miwa , T. M. Schmidt , P. Venezuela . MoS₂ on an amorphous HfO₂ surface: An ab initio investigation. J. Appl. Phys., 2015, 117( 19): 194303

[57] T. C. Nguyen , M. Otani , S. Okada . Semiconducting electronic property of graphene adsorbed on (0001) surfaces of SiO₂. Phys. Rev. Lett., 2011, 106( 10): 106801

[58] S. H. Feng , R. L. Yang , Z. Y. Jia , J. Y. Xiang , F. S. Wen , C. P. Mu , A. M. Nie , Z. S. Zhao , B. Xu , C. G. Tao , Y. J. Tian , Z. Y. Liu . Strain release induced novel fluorescence variation in CVD-grown monolayer WS₂ crystals. ACS Appl. Mater. Interfaces, 2017, 9( 39): 34071

[59] K. Keyshar , M. Berg , X. Zhang , R. Vajtai , G. Gupta , C. K. Chan , T. E. Beechem , P. M. Ajayan , A. D. Mohite , T. Ohta . Experimental determination of the ionization energies of MoSe₂, WS₂, and MoS₂ on SiO₂ using photoemission electron microscopy. ACS Nano, 2017, 11( 8): 8223

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant No. 11804115), the Foundation from Department of Science and Technology of Fujian Province (Grant Nos. 2019L3008, 2020J01704, 2021J01863, and 2021J05171), the Foundation from Department of Education of Fujian Province (Grant No. JT180261), and the Scientific Research Foundation from Jimei University (Grant Nos. ZC2018007, ZQ2019008, ZP2020066, and ZP2020065).

RIGHTS & PERMISSIONS

2022 Higher Education Press