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Robust n-type doping of WSe2 enabled by controllable proton irradiation

Haidong Liang1,3,§, Yue Zheng2,3,§, Leyi Loh4,§, Zehua Hu6, Qijie Liang7, Cheng Han2, Michel Bosman4( ), Wei Chen3,5,8( ), Andrew A. Bettiol1,3( )
Centre for Ion Beam Applications (CIBA), Department of Physics, National University of Singapore, Singapore 117542, Singapore
International Collaborative Laboratory of 2D Materials for Optoelectronics Science and Technology of Ministry of Education, Institute of Microscale Optoelectronics, Shenzhen University, Shenzhen 518060, China
Department of Physics, National University of Singapore, Singapore 117551, Singapore
Department of Materials Science and Engineering, National University of Singapore, Singapore 117575, Singapore
Department of Chemistry, National University of Singapore, Singapore 117543, Singapore
Division of Physics and Applied Physics, School of Physical and Mathematical Science, Nanyang Technological University, Singapore 637371, Singapore
Songshan Lake Materials Laboratory, Songshan Lake Mat Lab, Dongguan 523808, China
National University of Singapore (Suzhou) Research Institute, 377 Lin Quan Street, Suzhou Industrial Park, Suzhou 215123, China

§ Haidong Liang, Yue Zheng, and Leyi Loh contributed equally to this work.

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Graphical Abstract

Using high energy proton beam irradiation, we can consistently make n-type doping in WSe2 in a controlled ion fluence. The n-type doped WSe2 can stay as a n-type semiconductor for one year exposed to air.

Abstract

Two-dimensional (2D) transition metal dichalcogenides (TMDs) are considered to be promising building blocks for the next generation electronic and optoelectronic devices. Various doping schemes and work function engineering techniques have been explored to overcome the intrinsic performance limits of 2D TMDs. However, a reliable and long-time air stable doping scheme is still lacking in this field. In this work, we utilize keV ion beams of H2+ to irradiate layered WSe2 crystals and obtain efficient n-type doping effect for all irradiated crystals within a fluence of 1 × 1014 protons·cm−2 (1e14). Moreover, the irradiated WSe2 remains an n-type semiconductor even after it is exposed to ambient conditions for a year. Localized ion irradiation with a focused beam can directly pattern on the sample to make high performance homogenous p-n junction diodes. Raman and photoluminescence (PL) spectra demonstrate that the WSe2 crystal lattice stays intact after irradiation within 1e14. We attribute the reliable electron-doping to the significant increase in Se vacancies after the proton irradiation, which is confirmed by our scanning transmission electron microscope (STEM) results. Our work demonstrates a reliable and long-term air stable n-type doping scheme to realize high-performance electronic TMD devices, which is also suitable for further integration with other 2D devices.

Keywords

WSe2proton beam irradiationn-type dopinglong-time air stableSe vacancies

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References

[1]

Wang, Q. H.; Kalantar-Zadeh, K.; Kis, A.; Coleman, J. N.; Strano, M. S. Electronics and optoelectronics of two-dimensional transition metal dichalcogenides. Nat. Nanotechnol. 2012, 7, 699–712.
Crossref Google Scholar
[2]

Wang, H.; Yu, L. L.; Lee, Y. H.; Shi, Y. M.; Hsu, A.; Chin, M. L.; Li, L. J.; Dubey, M.; Kong, J.; Palacios, T. Integrated circuits based on bilayer MoS2 transistors. Nano Lett. 2012, 12, 4674–4680.
Crossref Google Scholar
[3]

Lee, Y. H.; Zhang, X. Q.; Zhang, W. J.; Chang, M. T.; Lin, C. T.; Chang, K. D.; Yu, Y. C.; Wang, J. T. W.; Chang, C. S.; Li, L. J. et al. Synthesis of large-area MoS2 atomic layers with chemical vapor deposition. Adv. Mater. 2012, 24, 2320–2325.
Crossref Google Scholar
[4]

Lee, G. H.; Yu, Y. J.; Cui, X.; Petrone, N.; Lee, C. H.; Choi, M. S.; Lee, D. Y.; Lee, C.; Yoo, W. J.; Watanabe, K. et al. Flexible and transparent MoS2 field-effect transistors on hexagonal boron nitride-graphene heterostructures. ACS Nano 2013, 7, 7931–7936.
Crossref Google Scholar
[5]

Akinwande, D.; Petrone, N.; Hone, J. Two-dimensional flexible nanoelectronics. Nat. Commun. 2014, 5, 5678.
Crossref Google Scholar
[6]

Liu, H.; Neal, A. T.; Ye, P. D. Channel length scaling of MoS2 MOSFETs. ACS Nano 2012, 6, 8563–8569.
Crossref Google Scholar
[7]

Shi, Y. M.; Li, H. N.; Li, L. J. Recent advances in controlled synthesis of two-dimensional transition metal dichalcogenides via vapour deposition techniques. Chem. Soc. Rev. 2015, 44, 2744–2756.
Crossref Google Scholar
[8]

Chen, M. L.; Sun, X. D.; Liu, H.; Wang, H. W.; Zhu, Q. B.; Wang, S. S.; Du, H. F.; Dong, B. J.; Zhang, J.; Sun, Y. et al. A FinFET with one atomic layer channel. Nat. Commun. 2020, 11, 1205.
Crossref Google Scholar
[9]

Liu, Y.; Duan, X. D.; Huang, Y.; Duan, X. F. Two-dimensional transistors beyond graphene and TMDCs. Chem. Soc. Rev. 2018, 47, 6388–6409.
Crossref Google Scholar
[10]

Long, M. S.; Wang, P.; Fang, H. H.; Hu, W. D. Progress, challenges, and opportunities for 2D material based photodetectors. Adv. Funct. Mater. 2019, 29, 1803807.
Crossref Google Scholar
[11]

Sun, Z. P.; Martinez, A.; Wang, F. Optical modulators with 2D layered materials. Nat. Photonics 2016, 10, 227–238.
Crossref Google Scholar
[12]

Withers, F.; Del Pozo-Zamudio, O.; Mishchenko, A.; Rooney, A. P.; Gholinia, A.; Watanabe, K.; Taniguchi, T.; Haigh, S. J.; Geim, A. K.; Tartakovskii, A. I. et al. Light-emitting diodes by band-structure engineering in van der Waals heterostructures. Nat. Mater. 2015, 14, 301–306.
Crossref Google Scholar
[13]

Yoo, H.; Heo, K.; Ansari, H. R.; Cho, S. Recent advances in electrical doping of 2D semiconductor materials: Methods, analyses, and applications. Nanomaterials 2021, 11, 832.
Crossref Google Scholar
[14]

Luo, P.; Zhuge, F. W.; Zhang, Q. F.; Chen, Y. Q.; Lv, L.; Huang, Y.; Li, H. Q.; Zhai, T. Y. Doping engineering and functionalization of two-dimensional metal chalcogenides. Nanoscale Horiz. 2019, 4, 26–51.
Crossref Google Scholar
[15]

Loh, L.; Zhang, Z. P.; Bosman, M.; Eda, G. Substitutional doping in 2D transition metal dichalcogenides. Nano Res. 2021, 14, 1668–1681.
Crossref Google Scholar
[16]

Cho, K.; Pak, J.; Chung, S.; Lee, T. Recent advances in interface engineering of transition-metal dichalcogenides with organic molecules and polymers. ACS Nano 2019, 13, 9713–9734.
Crossref Google Scholar
[17]

Schmidt, H.; Giustiniano, F.; Eda, G. Electronic transport properties of transition metal dichalcogenide field-effect devices: Surface and interface effects. Chem. Soc. Rev. 2015, 44, 7715–7736.
Crossref Google Scholar
[18]

Kiriya, D.; Tosun, M.; Zhao, P. D.; Kang, J. S.; Javey, A. Air-stable surface charge transfer doping of MoS2 by benzyl viologen. J. Am. Chem. Soc. 2014, 136, 7853–7856.
Crossref Google Scholar
[19]

Sim, D. M.; Kim, M.; Yim, S.; Choi, M. J.; Choi, J.; Yoo, S.; Jung, Y. S. Controlled doping of vacancy-containing few-layer MoS2 via highly stable thiol-based molecular chemisorption. ACS Nano 2015, 9, 12115–12123.
Crossref Google Scholar
[20]

Kang, D. H.; Shim, J.; Jang, S. K.; Jeon, J.; Jeon, M. H.; Yeom, G. Y.; Jung, W. S.; Jang, Y. H.; Lee, S.; Park, J. H. Controllable nondegenerate p-type doping of tungsten diselenide by octadecyltrichlorosilane. ACS Nano 2015, 9, 1099–1107.
Crossref Google Scholar
[21]

Benjamin, C. J.; Zhang, S.; Chen, Z. H. Controlled doping of transition metal dichalcogenides by metal work function tuning in phthalocyanine compounds. Nanoscale 2018, 10, 5148–5153.
Crossref Google Scholar
[22]

Pak, J.; Jang, J.; Cho, K.; Kim, T. Y.; Kim, J. K.; Song, Y.; Hong, W. K.; Min, M.; Lee, H.; Lee, T. Enhancement of photodetection characteristics of MoS2 field effect transistors using surface treatment with copper phthalocyanine. Nanoscale 2015, 7, 18780–18788.
Crossref Google Scholar
[23]

Mouri, S.; Miyauchi, Y.; Matsuda, K. Tunable photoluminescence of monolayer MoS2 via chemical doping. Nano Lett. 2013, 13, 5944–5948.
Crossref Google Scholar
[24]

Li, Y.; Xu, C. Y.; Hu, P. A.; Zhen, L. Carrier control of MoS2 nanoflakes by functional self-assembled monolayers. ACS Nano 2013, 7, 7795–7804.
Crossref Google Scholar
[25]

Dey, S.; Matte, H. S. S. R.; Shirodkar, S. N.; Waghmare, U. V.; Rao, C. N. R. Charge-transfer interaction between few-layer MoS2 and tetrathiafulvalene. Chem. -Asian J. 2013, 8, 1780–1784.
Crossref Google Scholar
[26]

Kang, D. H.; Kim, M. S.; Shim, J.; Jeon, J.; Park, H. Y.; Jung, W. S.; Yu, H. Y.; Pang, C. H.; Lee, S.; Park, J. H. High-performance transition metal dichalcogenide photodetectors enhanced by self-assembled monolayer doping. Adv. Funct. Mater. 2015, 25, 4219–4227.
Crossref Google Scholar
[27]

Tarasov, A.; Zhang, S. Y.; Tsai, M. Y.; Campbell, P. M.; Graham, S.; Barlow, S.; Marder, S. R.; Vogel, E. M. Controlled doping of large-area trilayer MoS2 with molecular reductants and oxidants. Adv. Mater. 2015, 27, 1175–1181.
Crossref Google Scholar
[28]

Andleeb, S.; Singh, A. K.; Eom, J. Chemical doping of MoS2 multilayer by p-toluene sulfonic acid. Sci. Technol. Adv. Mater. 2015, 16, 035009.
Crossref Google Scholar
[29]

Ghimire, G.; Dhakal, K. P.; Neupane, G. P.; Jo, S. G.; Kim, H.; Seo, C.; Lee, Y. H.; Joo, J.; Kim, J. Optically active charge transfer in hybrids of Alq3 nanoparticles and MoS2 monolayer. Nanotechnology 2017, 28, 185702.
Crossref Google Scholar
[30]

Heo, K.; Jo, S. H.; Shim, J.; Kang, D. H.; Kim, J. H.; Park, J. H. Stable and reversible triphenylphosphine-based n-type doping technique for molybdenum disulfide (MoS2). ACS Appl. Mater. Interfaces 2018, 10, 32765–32772.
Crossref Google Scholar
[31]

Peimyoo, N.; Yang, W. H.; Shang, J. Z.; Shen, X. N.; Wang, Y. L.; Yu, T. Chemically driven tunable light emission of charged and neutral excitons in monolayer WS2. ACS Nano 2014, 8, 11320–11329.
Crossref Google Scholar
[32]

Yoo, H.; Hong, S.; Moon, H.; On, S.; Ahn, H.; Lee, H. K.; Kim, S.; Hong, Y. K.; Kim, J. J. Chemical doping effects on CVD-grown multilayer MoSe2 transistor. Adv. Electron. Mater. 2018, 4, 1700639.
Crossref Google Scholar
[33]

Ghorbani-Asl, M.; Kretschmer, S.; Spearot, D. E.; Krasheninnikov, A. V. Two-dimensional MoS2 under ion irradiation: From controlled defect production to electronic structure engineering. 2D Mater. 2017, 4, 025078.
Crossref Google Scholar
[34]

Bertolazzi, S.; Bonacchi, S.; Nan, G. J.; Pershin, A.; Beljonne, D.; Samorì, P. Engineering chemically active defects in monolayer MoS2 transistors via ion-beam irradiation and their healing via vapor deposition of alkanethiols. Adv. Mater. 2017, 29, 1606760.
Crossref Google Scholar
[35]

Mupparapu, R.; Steinert, M.; George, A.; Tang, Z.; Turchanin, A.; Pertsch, T.; Staude, I. Facile resist-free nanopatterning of monolayers of MoS2 by focused ion-beam milling. Adv. Mater. Interfaces 2020, 7, 2000858.
Crossref Google Scholar
[36]

Madauß, L.; Ochedowski, O.; Lebius, H.; D’Etat, B. B.; Naylor, C. H.; Johnson, A. T. C.; Kotakoski, J.; Schleberger, M. Defect engineering of single- and few-layer MoS2 by swift heavy ion irradiation. 2D Mater. 2017, 4, 015034.
Crossref Google Scholar
[37]

Valerius, P.; Kretschmer, S.; Senkovskiy, B. V.; Wu, S. L.; Hall, J.; Herman, A.; Ehlen, N.; Ghorbani-Asl, M.; Grüneis, A.; Krasheninnikov, A. V. et al. Reversible crystalline-to-amorphous phase transformation in monolayer MoS2 under grazing ion irradiation. 2D Mater. 2020, 7, 025005.
Crossref Google Scholar
[38]

Choudhary, N.; Islam, M. R.; Kang, N.; Tetard, L.; Jung, Y.; Khondaker, S. I. Two-dimensional lateral heterojunction through bandgap engineering of MoS2 via oxygen plasma. J. Phys.: Condens. Matter 2016, 28, 364002.
Crossref Google Scholar
[39]

Chen, Y.; Huang, S. X.; Ji, X.; Adepalli, K.; Yin, K. D.; Ling, X.; Wang, X. W.; Xue, J. M.; Dresselhaus, M.; Kong, J. et al. Tuning electronic structure of single layer MoS2 through defect and interface engineering. ACS Nano 2018, 12, 2569–2579.
Crossref Google Scholar
[40]

Stanford, M. G.; Pudasaini, P. R.; Belianinov, A.; Cross, N.; Noh, J. H.; Koehler, M. R.; Mandrus, D. G.; Duscher, G.; Rondinone, A. J.; Ivanov, I. N. et al. Focused helium-ion beam irradiation effects on electrical transport properties of few-layer WSe2: Enabling nanoscale direct write homo-junctions. Sci. Rep. 2016, 6, 27276.
Crossref Google Scholar
[41]

He, Z. Y.; Zhao, R.; Chen, X. F.; Chen, H. J.; Zhu, Y. M.; Su, H. M.; Huang, S. X.; Xue, J. M.; Dai, J. F.; Cheng, S. et al. Defect engineering in single-layer MoS2 using heavy ion irradiation. ACS Appl. Mater. Interfaces 2018, 10, 42524–42533.
Crossref Google Scholar
[42]

Cheng, Z. H.; Abuzaid, H.; Yu, Y. F.; Zhang, F.; Li, Y. L.; Noyce, S. G.; Williams, N. X.; Lin, Y. C.; Doherty, J. L.; Tao, C. G. et al. Convergent ion beam alteration of 2D materials and metal-2D interfaces. 2D Mater. 2019, 6, 034005.
Crossref Google Scholar
[43]

Jadwiszczak, J.; Keane, D.; Maguire, P.; Cullen, C. P.; Zhou, Y. B.; Song, H. D.; Downing, C.; Fox, D.; McEvoy, N.; Zhu, R. et al. MoS2 memtransistors fabricated by localized helium ion beam irradiation. ACS Nano 2019, 13, 14262–14273.
Crossref Google Scholar
[44]

Komsa, H. P.; Kotakoski, J.; Kurasch, S.; Lehtinen, O.; Kaiser, U.; Krasheninnikov, A. V. Two-dimensional transition metal dichalcogenides under electron irradiation: Defect production and doping. Phys. Rev. Lett. 2012, 109, 035503.
Crossref Google Scholar
[45]

Gao, L.; Liao, Q. L.; Zhang, X. K.; Liu, X. Z.; Gu, L.; Liu, B. S.; Du, J. L.; Ou, Y.; Xiao, J. K.; Kang, Z. et al. Defect-engineered atomically thin MoS2 homogeneous electronics for logic inverters. Adv. Mater. 2020, 32, 1906646.
Crossref Google Scholar
[46]

Stanford, M. G.; Pudasaini, P. R.; Gallmeier, E. T.; Cross, N.; Liang, L. B.; Oyedele, A.; Duscher, G.; Mahjouri-Samani, M.; Wang, K.; Xiao, K. et al. High conduction hopping behavior induced in transition metal dichalcogenides by percolating defect networks: Toward atomically thin circuits. Adv. Funct. Mater. 2017, 27, 1702829.
Crossref Google Scholar
[47]

Li, Z. Q.; Chen, F. Ion beam modification of two-dimensional materials: Characterization, properties, and applications. Appl. Phys. Rev. 2017, 4, 011103.
Crossref Google Scholar
[48]

Fox, D. S.; Zhou, Y. B.; Maguire, P.; O’Neill, A.; Ó’Coileaín, C.; Gatensby, R.; Glushenkov, A. M.; Tao, T.; Duesberg, G. S.; Shvets, I. V.; Abid, M. et al. Nanopatterning and electrical tuning of MoS2 layers with a subnanometer helium ion beam. Nano Lett. 2015, 15, 5307–5313.
Crossref Google Scholar
[49]

Kim, T. Y.; Cho, K.; Park, W.; Park, J.; Song, Y.; Hong, S.; Hong, W. K.; Lee, T. Irradiation effects of high-energy proton beams on MoS2 field effect transistors. ACS Nano 2014, 8, 2774–2781.
Crossref Google Scholar
[50]

Tosun, M.; Chan, L.; Amani, M.; Roy, T.; Ahn, G. H.; Taheri, P.; Carraro, C.; Ager, J. W.; Maboudian, R.; Javey, A. Air-stable n-doping of WSe2 by anion vacancy formation with mild plasma treatment. ACS Nano 2016, 10, 6853–6860.
Crossref Google Scholar
[51]

Wang, S. F.; Zhao, W. J.; Giustiniano, F.; Eda, G. Effect of oxygen and ozone on p-type doping of ultra-thin WSe2 and MoSe2 field effect transistors. Phys. Chem. Chem. Phys. 2016, 18, 4304–4309.
Crossref Google Scholar
[52]

Jones, A. M.; Yu, H. Y.; Ghimire, N. J.; Wu, S. F.; Aivazian, G.; Ross, J. S.; Zhao, B.; Yan, J. Q.; Mandrus, D. G.; Xiao, D. et al. Optical generation of excitonic valley coherence in monolayer WSe2. Nat. Nanotechnol. 2013, 8, 634–638.
Crossref Google Scholar
[53]

Wang, Y. L.; Cong, C. X.; Yang, W. H.; Shang, J. Z.; Peimyoo, N.; Chen, Y.; Kang, J. Y.; Wang, J. P.; Huang, W.; Yu, T. Strain-induced direct-indirect bandgap transition and phonon modulation in monolayer WS2. Nano Res. 2015, 8, 2562–2572.
Crossref Google Scholar
[54]
Zhu, C. R ; Zhang, K.; Glazov, M.; Urbaszek, B.; Amand, T.; Ji, Z. W.; Liu, B. L.; Marie, X. Exciton valley dynamics probed by Kerr rotation in WSe2 monolayers. Phys. Rev. B 2014, 90, 161302(R).
[55]

Ye, Y. X.; Dou, X. M.; Ding, K.; Jiang, D. S.; Yang, F. H.; Sun, B. Q. Pressure-induced K–Λ crossing in monolayer WSe2. Nanoscale 2016, 8, 10843–10848.
Crossref Google Scholar
[56]

Zheng, Y. J.; Chen, Y. F.; Huang, Y. L.; Gogoi, P. K.; Li, M. Y.; Li, L. J.; Trevisanutto, P. E.; Wang, Q. X.; Pennycook, S. J.; Wee, A. T. S. et al. Point defects and localized excitons in 2D WSe2. ACS Nano 2019, 13, 6050–6059.
Crossref Google Scholar
[57]

Zhang, S.; Wang, C. G.; Li, M. Y.; Huang, D.; Li, L. J.; Ji, W.; Wu, S. W. Defect structure of localized excitons in a WSe2 monolayer. Phys. Rev. Lett. 2017, 119, 046101.
Crossref Google Scholar
Nano Research
Volume 16 Issue 1,
January 2023
Pages 1220-1227
DOI: 10.1007/s12274-022-4668-9
Cite this article:
Liang H, Zheng Y, Loh L, et al. Robust n-type doping of WSe2 enabled by controllable proton irradiation. Nano Research, 2023, 16(1): 1220-1227. https://doi.org/10.1007/s12274-022-4668-9
Topics:
CMOS integrated circuitsDefectsField effect transistorsIrradiationLayered semiconductorsNanoelectronics Semiconductor device manufacture Semiconductor devices Semiconductor dopingThin film transistors

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Received: 13 May 2022
Revised: 09 June 2022
Accepted: 15 June 2022
Published: 27 August 2022
© Tsinghua University Press 2022
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