Enhanced Exciton-to-Trion Conversion by Proton Irradiation of Atomically Thin WS2

Wang, Xuejing; Pettes, Michael Thompson; Wang, Yongqiang; Zhu, Jian-Xin; Dhall, Rohan; Song, Chengyu; Jones, Andrew Crandall; Ciston, Jim; Yoo, Jinkyoung

doi:10.1021/acs.nanolett.2c04987

Title: Enhanced Exciton-to-Trion Conversion by Proton Irradiation of Atomically Thin WS₂

Journal Article · 24 April 2023 · Nano Letters

DOI: https://doi.org/10.1021/acs.nanolett.2c04987 · OSTI ID:1987395

^[1];

^[1]; Dhall, Rohan ^[2]; Song, Chengyu ^[2];

^[1]; Ciston, Jim ^[2];

^[1]

Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Defect engineering of van der Waals semiconductors has been demonstrated as an effective approach to manipulate the structural and functional characteristics toward dynamic device controls, yet correlations between physical properties with defect evolution remain underexplored. Here, using proton irradiation, we observe an enhanced exciton-to-trion conversion of the atomically thin WS₂. The altered excitonic states are closely correlated with nanopore induced atomic displacement, W nanoclusters, and zigzag edge terminations, verified by scanning transmission electron microscopy, photoluminescence, and Raman spectroscopy. Density functional theory calculation suggests that nanopores facilitate formation of in-gap states that act as sinks for free electrons to couple with excitons. The ion energy loss simulation predicts a dominating electron ionization effect upon proton irradiation, providing further evidence on band perturbations and nanopore formation without destroying the overall crystallinity. This study provides a route in tuning the excitonic properties of van der Waals semiconductors using an irradiation-based defect engineering approach.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: 89233218CNA000001; AC02-05CH11231

OSTI ID:: 1987395

Alternate ID(s):: OSTI ID: 2407289

Report Number(s):: LA-UR-22-29441

Journal Information:: Nano Letters, Vol. 23, Issue 9; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (75)

Are two-dimensional materials radiation tolerant? Krasheninnikov, Arkady V. Nanoscale Horizons, Vol. 5, Issue 11 https://doi.org/10.1039/D0NH00465K	journal	January 2020
Trion formation dynamics in monolayer transition metal dichalcogenides Singh, Akshay; Moody, Galan; Tran, Kha Physical Review B, Vol. 93, Issue 4 https://doi.org/10.1103/PhysRevB.93.041401	journal	January 2016
Activating and optimizing MoS2 basal planes for hydrogen evolution through the formation of strained sulphur vacancies Li, Hong; Tsai, Charlie; Koh, Ai Leen Nature Materials, Vol. 15, Issue 1 https://doi.org/10.1038/nmat4465	journal	November 2015
Observation of zigzag and armchair edges of graphite using scanning tunneling microscopy and spectroscopy Kobayashi, Yousuke; Fukui, Ken-ichi; Enoki, Toshiaki Physical Review B, Vol. 71, Issue 19 https://doi.org/10.1103/PhysRevB.71.193406	journal	May 2005
Robust valley polarization of helium ion modified atomically thin MoS ₂ Klein, J.; Kuc, A.; Nolinder, A. 2D Materials, Vol. 5, Issue 1 https://doi.org/10.1088/2053-1583/aa9642	journal	November 2017
Van der Waals heterostructures for spintronics and opto-spintronics Sierra, Juan F.; Fabian, Jaroslav; Kawakami, Roland K. Nature Nanotechnology, Vol. 16, Issue 8 https://doi.org/10.1038/s41565-021-00936-x	journal	July 2021
Atomic-Scale Carving of Nanopores into a van der Waals Heterostructure with Slow Highly Charged Ions Schwestka, Janine; Inani, Heena; Tripathi, Mukesh ACS Nano, Vol. 14, Issue 8 https://doi.org/10.1021/acsnano.0c04476	journal	July 2020
Introduction rates and annealing of defects in ion-implanted SiO2 layers on Si EerNisse, E. P.; Norris, C. B. Journal of Applied Physics, Vol. 45, Issue 12 https://doi.org/10.1063/1.1663215	journal	December 1974
Magnetic edge states in MoS 2 characterized using density-functional theory Vojvodic, Aleksandra; Hinnemann, Berit; Nørskov, Jens K. Physical Review B, Vol. 80, Issue 12 https://doi.org/10.1103/PhysRevB.80.125416	journal	September 2009
Locally defined quantum emission from epitaxial few-layer tungsten diselenide Wu, Wei; Dass, Chandriker K.; Hendrickson, Joshua R. Applied Physics Letters, Vol. 114, Issue 21 https://doi.org/10.1063/1.5091779	journal	May 2019
Identification of excitons, trions and biexcitons in single-layer WS ₂ : Identification of excitons, trions and biexcitons in single-layer WS Plechinger, Gerd; Nagler, Philipp; Kraus, Julia physica status solidi (RRL) - Rapid Research Letters, Vol. 9, Issue 8 https://doi.org/10.1002/pssr.201510224	journal	July 2015
Trion fine structure and coupled spin–valley dynamics in monolayer tungsten disulfide Plechinger, Gerd; Nagler, Philipp; Arora, Ashish Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms12715	journal	September 2016
In situ edge engineering in two-dimensional transition metal dichalcogenides Sang, Xiahan; Li, Xufan; Zhao, Wen Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04435-x	journal	May 2018
Effects of Defects on Band Structure and Excitons in WS ₂ Revealed by Nanoscale Photoemission Spectroscopy Kastl, Christoph; Koch, Roland J.; Chen, Christopher T. ACS Nano https://doi.org/10.1021/acsnano.8b06574	journal	January 2019
Selective Engineering of Chalcogen Defects in MoS ₂ by Low-Energy Helium Plasma Huang, Binjie; Tian, Feng; Shen, Youde ACS Applied Materials & Interfaces, Vol. 11, Issue 27 https://doi.org/10.1021/acsami.9b05507	journal	June 2019
Optical tuning of exciton and trion emissions in monolayer phosphorene Yang, Jiong; Xu, Renjing; Pei, Jiajie Light: Science & Applications, Vol. 4, Issue 7 https://doi.org/10.1038/lsa.2015.85	journal	July 2015
Identification of individual and few layers of WS2 using Raman Spectroscopy Berkdemir, Ayse; Gutiérrez, Humberto R.; Botello-Méndez, Andrés R. Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep01755	journal	April 2013
Emergent Multifunctional Magnetic Proximity in van der Waals Layered Heterostructures Choi, Eun‐Mi; Sim, Kyung Ik; Burch, Kenneth S. Advanced Science, Vol. 9, Issue 21 https://doi.org/10.1002/advs.202200186	journal	May 2022
Spatially Controlled Fabrication and Mechanisms of Atomically Thin Nanowell Patterns in Bilayer WS₂ Using in Situ High Temperature Electron Microscopy Chen, Jun; Ryu, Gyeong Hee; Zhang, Qianyang ACS Nano, Vol. 13, Issue 12 https://doi.org/10.1021/acsnano.9b08220	journal	December 2019
MoS ₂ Nanoribbons: High Stability and Unusual Electronic and Magnetic Properties Li, Yafei; Zhou, Zhen; Zhang, Shengbai Journal of the American Chemical Society, Vol. 130, Issue 49 https://doi.org/10.1021/ja805545x	journal	December 2008
Spin-Valley Locking Effect in Defect States of Monolayer MoS ₂ Wang, Yaqian; Deng, Longjiang; Wei, Qilin Nano Letters, Vol. 20, Issue 3 https://doi.org/10.1021/acs.nanolett.0c00138	journal	February 2020
Deterministic strain-induced arrays of quantum emitters in a two-dimensional semiconductor Branny, Artur; Kumar, Santosh; Proux, Raphaël Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15053	journal	May 2017
Edge modes in zigzag and armchair ribbons of monolayer MoS ₂ Rostami, Habib; Asgari, Reza; Guinea, Francisco Journal of Physics: Condensed Matter, Vol. 28, Issue 49 https://doi.org/10.1088/0953-8984/28/49/495001	journal	October 2016
Exciton physics and device application of two-dimensional transition metal dichalcogenide semiconductors Mueller, Thomas; Malic, Ermin npj 2D Materials and Applications, Vol. 2, Issue 1 https://doi.org/10.1038/s41699-018-0074-2	journal	September 2018
Defect engineering of two-dimensional transition metal dichalcogenides Lin, Zhong; Carvalho, Bruno R.; Kahn, Ethan 2D Materials, Vol. 3, Issue 2 https://doi.org/10.1088/2053-1583/3/2/022002	journal	April 2016
Site-controlled telecom-wavelength single-photon emitters in atomically-thin MoTe2 Zhao, Huan; Pettes, Michael T.; Zheng, Yu Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-27033-w	journal	November 2021
Precise control of the interlayer twist angle in large scale MoS2 homostructures Liao, Mengzhou; Wei, Zheng; Du, Luojun Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-16056-4	journal	May 2020
Nanopores in 2D MoS ₂ : Defect-Mediated Formation and Density Modulation Ke, Jian-An; Garaj, Slaven; Gradečak, Silvija ACS Applied Materials & Interfaces, Vol. 11, Issue 29 https://doi.org/10.1021/acsami.9b03531	journal	June 2019
Defect Engineering in Single-Layer MoS ₂ Using Heavy Ion Irradiation He, Zuyun; Zhao, Ran; Chen, Xiaofei ACS Applied Materials & Interfaces, Vol. 10, Issue 49 https://doi.org/10.1021/acsami.8b17145	journal	November 2018
2D materials for quantum information science Liu, Xiaolong; Hersam, Mark C. Nature Reviews Materials, Vol. 4, Issue 10 https://doi.org/10.1038/s41578-019-0136-x	journal	August 2019
From Bulk to Monolayer MoS2: Evolution of Raman Scattering Li, Hong; Zhang, Qing; Yap, Chin Chong Ray Advanced Functional Materials, Vol. 22, Issue 7 https://doi.org/10.1002/adfm.201102111	journal	January 2012
Investigation of multilayer WS2 flakes as charge trapping stack layers in non-volatile memories Wang, Hong; Ren, Deliang; Lu, Chao Applied Physics Letters, Vol. 112, Issue 23 https://doi.org/10.1063/1.5024799	journal	June 2018
Excitons and emergent quantum phenomena in stacked 2D semiconductors Wilson, Nathan P.; Yao, Wang; Shan, Jie Nature, Vol. 599, Issue 7885 https://doi.org/10.1038/s41586-021-03979-1	journal	November 2021
Two-dimensional material nanophotonics Xia, Fengnian; Wang, Han; Xiao, Di Nature Photonics, Vol. 8, Issue 12 https://doi.org/10.1038/nphoton.2014.271	journal	November 2014
Defects activated photoluminescence in two-dimensional semiconductors: interplay between bound, charged and free excitons Tongay, Sefaattin; Suh, Joonki; Ataca, Can Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep02657	journal	September 2013
Control of trion-to-exciton conversion in monolayer WS ₂ by orbital angular momentum of light Kesarwani, Rahul; Simbulan, Kristan Bryan; Huang, Teng-De Science Advances, Vol. 8, Issue 13 https://doi.org/10.1126/sciadv.abm0100	journal	April 2022
Angstrom-Size Defect Creation and Ionic Transport through Pores in Single-Layer MoS 2 Thiruraman, Jothi Priyanka; Fujisawa, Kazunori; Danda, Gopinath Nano Letters, Vol. 18, Issue 3 https://doi.org/10.1021/acs.nanolett.7b04526	journal	February 2018
The Role of Oxygen Atoms on Excitons at the Edges of Monolayer WS ₂ Hu, Zhenliang; Avila, Jose; Wang, Xinyun Nano Letters, Vol. 19, Issue 7 https://doi.org/10.1021/acs.nanolett.9b01670	journal	June 2019
Enhanced Trion Emission in Monolayer MoSe ₂ by Constructing a Type‐I Van Der Waals Heterostructure Duan, Juanmei; Chava, Phanish; Ghorbani‐Asl, Mahdi Advanced Functional Materials, Vol. 31, Issue 40 https://doi.org/10.1002/adfm.202104960	journal	July 2021
Defect Heterogeneity in Monolayer WS ₂ Unveiled by Work Function Variance Wang, Xinyun; Dan, Jiadong; Hu, Zhenliang Chemistry of Materials, Vol. 31, Issue 19 https://doi.org/10.1021/acs.chemmater.9b02157	journal	August 2019
Exciton-to-trion conversion as a control mechanism for valley polarization in room-temperature monolayer WS2 Carmiggelt, Joris J.; Borst, Michael; van der Sar, Toeno Scientific Reports, Vol. 10, Issue 1 https://doi.org/10.1038/s41598-020-74376-3	journal	October 2020
Observation of Tunable Charged Exciton Polaritons in Hybrid Monolayer WS ₂ −Plasmonic Nanoantenna System Cuadra, Jorge; Baranov, Denis G.; Wersäll, Martin Nano Letters, Vol. 18, Issue 3 https://doi.org/10.1021/acs.nanolett.7b04965	journal	January 2018
Defect Engineering of Two-Dimensional Transition-Metal Dichalcogenides: Applications, Challenges, and Opportunities Liang, Qijie; Zhang, Qian; Zhao, Xiaoxu ACS Nano, Vol. 15, Issue 2 https://doi.org/10.1021/acsnano.0c09666	journal	January 2021
Robust and High Photoluminescence in WS ₂ Monolayer through In Situ Defect Engineering Cui, Qilong; Luo, Ziyu; Cui, Qirui Advanced Functional Materials, Vol. 31, Issue 38 https://doi.org/10.1002/adfm.202105339	journal	July 2021
Emergence of Highly Linearly Polarized Interlayer Exciton Emission in MoSe ₂ /WSe ₂ Heterobilayers with Transfer-Induced Layer Corrugation Alexeev, Evgeny M.; Mullin, Nic; Ares, Pablo ACS Nano, Vol. 14, Issue 9 https://doi.org/10.1021/acsnano.0c01146	journal	August 2020
Quantum emission from hexagonal boron nitride monolayers Tran, Toan Trong; Bray, Kerem; Ford, Michael J. Nature Nanotechnology, Vol. 11, Issue 1 https://doi.org/10.1038/nnano.2015.242	journal	October 2015
Atomically thin quantum light-emitting diodes Palacios-Berraquero, Carmen; Barbone, Matteo; Kara, Dhiren M. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms12978	journal	September 2016
Defect engineering of single- and few-layer MoS ₂ by swift heavy ion irradiation Madauß, Lukas; Ochedowski, Oliver; Lebius, Henning 2D Materials, Vol. 4, Issue 1 https://doi.org/10.1088/2053-1583/4/1/015034	journal	December 2016
Macroscopic and microscopic effects of radiation in amorphous SiO2 Devine, R. A. B. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 91, Issue 1-4 https://doi.org/10.1016/0168-583X(94)96253-7	journal	June 1994
Defect Dynamics in 2-D MoS ₂ Probed by Using Machine Learning, Atomistic Simulations, and High-Resolution Microscopy Patra, Tarak K.; Zhang, Fu; Schulman, Daniel S. ACS Nano, Vol. 12, Issue 8 https://doi.org/10.1021/acsnano.8b02844	journal	July 2018
Tuning Electronic Structure of Single Layer MoS ₂ through Defect and Interface Engineering Chen, Yan; Huang, Shengxi; Ji, Xiang ACS Nano, Vol. 12, Issue 3 https://doi.org/10.1021/acsnano.7b08418	journal	February 2018
Laser-induced fabrication of nanoporous monolayer WS ₂ membranes Danda, Gopinath; Masih Das, Paul; Drndić, Marija 2D Materials, Vol. 5, Issue 3 https://doi.org/10.1088/2053-1583/aabb73	journal	April 2018
Voltage-controlled quantum light from an atomically thin semiconductor Chakraborty, Chitraleema; Kinnischtzke, Laura; Goodfellow, Kenneth M. Nature Nanotechnology, Vol. 10, Issue 6 https://doi.org/10.1038/nnano.2015.79	journal	May 2015
Photonics and optoelectronics of 2D semiconductor transition metal dichalcogenides Mak, Kin Fai; Shan, Jie Nature Photonics, Vol. 10, Issue 4 https://doi.org/10.1038/nphoton.2015.282	journal	March 2016
Exciton Transitions in Monolayer WS₂ Activated by Swift Heavy Ion Irradiation Zhang, Shengxia; Hu, Peipei; Xu, Lijun The Journal of Physical Chemistry C, Vol. 125, Issue 37 https://doi.org/10.1021/acs.jpcc.1c04724	journal	September 2021
2D transition metal dichalcogenides Manzeli, Sajedeh; Ovchinnikov, Dmitry; Pasquier, Diego Nature Reviews Materials, Vol. 2, Issue 8 https://doi.org/10.1038/natrevmats.2017.33	journal	June 2017
Effect of disorder on Raman scattering of single-layer Mo S 2 Mignuzzi, Sandro; Pollard, Andrew J.; Bonini, Nicola Physical Review B, Vol. 91, Issue 19 https://doi.org/10.1103/PhysRevB.91.195411	journal	May 2015
Single quantum emitters in monolayer semiconductors He, Yu-Ming; Clark, Genevieve; Schaibley, John R. Nature Nanotechnology, Vol. 10, Issue 6 https://doi.org/10.1038/nnano.2015.75	journal	May 2015
Atomic mechanism of the semiconducting-to-metallic phase transition in single-layered MoS2 Lin, Yung-Chang; Dumcenco, Dumitru O.; Huang, Ying-Sheng Nature Nanotechnology, Vol. 9, Issue 5 https://doi.org/10.1038/nnano.2014.64	journal	April 2014
Promises and prospects of two-dimensional transistors Liu, Yuan; Duan, Xidong; Shin, Hyeon-Jin Nature, Vol. 591, Issue 7848 https://doi.org/10.1038/s41586-021-03339-z	journal	March 2021
Electrically Switchable Chiral Light-Emitting Transistor Zhang, Y. J.; Oka, T.; Suzuki, R. Science, Vol. 344, Issue 6185 https://doi.org/10.1126/science.1251329	journal	April 2014
Probing the origin of excitonic states in monolayer WSe2 Huang, Jiani; Hoang, Thang B.; Mikkelsen, Maiken H. Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep22414	journal	March 2016
Direct Imaging of Individual Molecular Binding to Clean Nanopore Edges in 2D Monolayer MoS₂ Gerkman, Mihael A.; Lee, Ja Kyung; Li, Xiang ACS Nano, Vol. 14, Issue 1 https://doi.org/10.1021/acsnano.9b06061	journal	November 2019
Tightly bound trions in monolayer MoS2 Mak, Kin Fai; He, Keliang; Lee, Changgu Nature Materials, Vol. 12, Issue 3 https://doi.org/10.1038/nmat3505	journal	December 2012
Edge-states ferromagnetism of WS ₂ nanosheets Huo, Nengjie; Li, Yan; Kang, Jun Applied Physics Letters, Vol. 104, Issue 20 https://doi.org/10.1063/1.4875582	journal	May 2014
The Dielectric Impact of Layer Distances on Exciton and Trion Binding Energies in van der Waals Heterostructures Florian, Matthias; Hartmann, Malte; Steinhoff, Alexander Nano Letters, Vol. 18, Issue 4 https://doi.org/10.1021/acs.nanolett.8b00840	journal	March 2018
Radiation Effects in MOS Oxides Schwank, James R.; Shaneyfelt, Marty R.; Fleetwood, Daniel M. IEEE Transactions on Nuclear Science, Vol. 55, Issue 4 https://doi.org/10.1109/TNS.2008.2001040	journal	August 2008
Ultrasensitive photodetectors based on monolayer MoS2 Lopez-Sanchez, Oriol; Lembke, Dominik; Kayci, Metin Nature Nanotechnology, Vol. 8, Issue 7 https://doi.org/10.1038/nnano.2013.100	journal	June 2013
Radiation-induced direct bandgap transition in few-layer MoS ₂ Wang, Bo; Yang, Sisi; Chen, Jihan Applied Physics Letters, Vol. 111, Issue 13 https://doi.org/10.1063/1.5005121	journal	September 2017
Intrinsic Structural Defects in Monolayer Molybdenum Disulfide Zhou, Wu; Zou, Xiaolong; Najmaei, Sina Nano Letters, Vol. 13, Issue 6, p. 2615-2622 https://doi.org/10.1021/nl4007479	journal	May 2013
Electron radiation damage mechanisms in 2D MoSe ₂ Lehnert, T.; Lehtinen, O.; Algara–Siller, G. Applied Physics Letters, Vol. 110, Issue 3 https://doi.org/10.1063/1.4973809	journal	January 2017
Two-dimensional flexible nanoelectronics Akinwande, Deji; Petrone, Nicholas; Hone, James Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms6678	journal	December 2014
Valleytronics in 2D materials Schaibley, John R.; Yu, Hongyi; Clark, Genevieve Nature Reviews Materials, Vol. 1, Issue 11 https://doi.org/10.1038/natrevmats.2016.55	journal	August 2016
Theory of neutral and charged excitons in monolayer transition metal dichalcogenides Berkelbach, Timothy C.; Hybertsen, Mark S.; Reichman, David R. Physical Review B, Vol. 88, Issue 4 https://doi.org/10.1103/PhysRevB.88.045318	journal	July 2013
The role of chalcogen vacancies for atomic defect emission in MoS2 Mitterreiter, Elmar; Schuler, Bruno; Micevic, Ana Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-24102-y	journal	June 2021

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Related Subjects

77 NANOSCIENCE AND NANOTECHNOLOGY
defects
defects in solids
excitons
irradiation
nanopores
defect engineering
proton irradiation
transition metal dichalcogenides (TMDs)
excitonic property

Title: Enhanced Exciton-to-Trion Conversion by Proton Irradiation of Atomically Thin WS2

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Title: Enhanced Exciton-to-Trion Conversion by Proton Irradiation of Atomically Thin WS₂