Laser-Assisted Synthesis of Monolayer 2D MoSe2 Crystals with Tunable Vacancy Concentrations: Implications for Gas and Biosensing

Azam, Nurul; Boebinger, Matthew G.; Jaiswal, Suman; Unocic, Raymond R.; Fathi-Hafshejani, Parvin; Mahjouri-Samani, Masoud

doi:10.1021/acsanm.2c01458

Title: Laser-Assisted Synthesis of Monolayer 2D MoSe₂ Crystals with Tunable Vacancy Concentrations: Implications for Gas and Biosensing

Journal Article · Wed Jun 29 00:00:00 EDT 2022 · ACS Applied Nano Materials

DOI:https://doi.org/10.1021/acsanm.2c01458· OSTI ID:1883659

^[1];

^[2]; Jaiswal, Suman ^[1];

^[2]; Fathi-Hafshejani, Parvin ^[1];

^[1]

Auburn University, AL (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

We report tuning the structural and electronic properties of atomically thin two-dimensional (2D) materials via defect and vacancy engineering is the key to enabling their potential use in various applications, including electronics, energy, and sensing devices. Vacancies are, for instance, becoming highly promising for the enhanced interaction of gases and biomolecules with 2D materials in energy and sensing applications. However, the deterministic generation of desirable vacancies with tunable concentrations remains a challenge in 2D materials due to the limitations in the current growth methods, such as the complex reaction chemistries and gas flow dynamics. Therefore, engineering defects and vacancies in 2D materials have been mainly limited to destructive top-down processes such as heating, ion bombardments, and laser postprocessing. Here, we introduce a single-step bottom-up synthesis approach for the growth of monolayer MoSe₂ crystals with tunable vacancy concentrations. This method utilizes the spatiotemporal properties and adjustable power densities of the lasers to control the vaporization dynamics of the stoichiometric MoSe₂ powders. Such a mechanism in the vaporization allows us to grow tunable stoichiometry monolayer MoSe_2–x crystals on the substrates. The localized and time-controlled (250 ms to 2 s) vaporization of the MoSe₂ powder by a CO₂ laser enables the formation of monolayer crystals with controlled vacancy concentrations ranging from ~1 to 20%. The effects of laser power, laser irradiation time, and background pressure on the tuning range and subsequent properties of the crystals are investigated and quantified using Raman and photoluminescence spectroscopy, scanning transmission electron microscopy (STEM), and time-correlated single-photon counting (TCSPC). This bottom-up synthesis is a promising approach that allows the deterministic vacancy tuning for future electronics and, in particular, gas and biosensing applications without the need for further postprocessing and potential structural disruption of the crystals.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC); National Science Foundation (NSF)

Grant/Contract Number:: AC05-00OR22725; 1923363

OSTI ID:: 1883659

Journal Information:: ACS Applied Nano Materials, Vol. 5, Issue 7; ISSN 2574-0970

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (68)

Interfacial Thermal Conductance between Monolayer WSe ₂ and SiO ₂ under Consideration of Radiative Electron–Hole Recombination Hunter, Nicholas; Azam, Nurul; Zobeiri, Hamidreza ACS Applied Materials & Interfaces, Vol. 12, Issue 45 https://doi.org/10.1021/acsami.0c14990	journal	October 2020
Helium-ion-beam nanofabrication: extreme processes and applications He, Shixuan; Tian, Rong; Wu, Wei International Journal of Extreme Manufacturing, Vol. 3, Issue 1 https://doi.org/10.1088/2631-7990/abc673	journal	January 2021
Two-dimensional spintronics for low-power electronics Lin, Xiaoyang; Yang, Wei; Wang, Kang L. Nature Electronics, Vol. 2, Issue 7 https://doi.org/10.1038/s41928-019-0273-7	journal	July 2019
Solid-state single-photon emitters Aharonovich, Igor; Englund, Dirk; Toth, Milos Nature Photonics, Vol. 10, Issue 10 https://doi.org/10.1038/nphoton.2016.186	journal	September 2016
Two-dimensional materials under electron irradiation Sun, Litao; Banhart, Florian; Warner, Jamie MRS Bulletin, Vol. 40, Issue 1 https://doi.org/10.1557/mrs.2014.303	journal	January 2015
A low-power biomimetic collision detector based on an in-memory molybdenum disulfide photodetector Jayachandran, Darsith; Oberoi, Aaryan; Sebastian, Amritanand Nature Electronics, Vol. 3, Issue 10 https://doi.org/10.1038/s41928-020-00466-9	journal	August 2020
Atomic Defects in Two-Dimensional Materials: From Single-Atom Spectroscopy to Functionalities in Opto-/Electronics, Nanomagnetism, and Catalysis Hong, Jinhua; Jin, Chuanhong; Yuan, Jun Advanced Materials, Vol. 29, Issue 14 https://doi.org/10.1002/adma.201606434	journal	March 2017
Quantifying Defects in Graphene via Raman Spectroscopy at Different Excitation Energies Cançado, L. G.; Jorio, A.; Ferreira, E. H. Martins Nano Letters, Vol. 11, Issue 8, p. 3190-3196 https://doi.org/10.1021/nl201432g	journal	July 2011
Photochemical Reaction in Monolayer MoS ₂ via Correlated Photoluminescence, Raman Spectroscopy, and Atomic Force Microscopy Oh, Hye Min; Han, Gang Hee; Kim, Hyun ACS Nano, Vol. 10, Issue 5 https://doi.org/10.1021/acsnano.6b00895	journal	April 2016
Engineering and probing atomic quantum defects in 2D semiconductors: A perspective Robinson, Joshua A.; Schuler, Bruno Applied Physics Letters, Vol. 119, Issue 14 https://doi.org/10.1063/5.0065185	journal	October 2021
Neutralizing Defect States in MoS₂ Monolayers Huang, Xiaheng; Li, Zidong; Liu, Xiao ACS Applied Materials & Interfaces, Vol. 13, Issue 37 https://doi.org/10.1021/acsami.1c07956	journal	August 2021
Two-dimensional transition metal dichalcogenides: interface and defect engineering Hu, Zehua; Wu, Zhangting; Han, Cheng Chemical Society Reviews, Vol. 47, Issue 9 https://doi.org/10.1039/C8CS00024G	journal	January 2018
Spotting the differences in two-dimensional materials – the Raman scattering perspective Zhang, Shishu; Zhang, Na; Zhao, Yan Chemical Society Reviews, Vol. 47, Issue 9 https://doi.org/10.1039/C7CS00874K	journal	January 2018
Atomistic defects as single-photon emitters in atomically thin MoS ₂ Barthelmi, K.; Klein, J.; Hötger, A. Applied Physics Letters, Vol. 117, Issue 7 https://doi.org/10.1063/5.0018557	journal	August 2020
Enhancement of Out-of-Plane Charge Transport in a Vertically Stacked Two-Dimensional Heterostructure Using Point Defects Liu, Yanran; Gao, Zhibin; Tan, Yang ACS Nano, Vol. 12, Issue 10 https://doi.org/10.1021/acsnano.8b06503	journal	September 2018
In-situ coalesced vacancies on MoSe2 mimicking noble metal: Unprecedented Tafel reaction in hydrogen evolution Lee, Junghyun; Kim, Changmin; Choi, KeunSu Nano Energy, Vol. 63 https://doi.org/10.1016/j.nanoen.2019.06.042	journal	September 2019
Atomic level deposition to extend Moore’s law and beyond Chen, Rong; Li, Yi-Cheng; Cai, Jia-Ming International Journal of Extreme Manufacturing, Vol. 2, Issue 2 https://doi.org/10.1088/2631-7990/ab83e0	journal	April 2020
Line Defects in Molybdenum Disulfide Layers Enyashin, Andrey N.; Bar-Sadan, Maya; Houben, Lothar The Journal of Physical Chemistry C, Vol. 117, Issue 20 https://doi.org/10.1021/jp403976d	journal	May 2013
Fundamentals of atomic and close-to-atomic scale manufacturing: a review Gao, Jian; Luo, Xichun; Fang, Fengzhou International Journal of Extreme Manufacturing, Vol. 4, Issue 1 https://doi.org/10.1088/2631-7990/ac3bb2	journal	December 2021
Defect Engineering in 2D Materials: Precise Manipulation and Improved Functionalities Jiang, Jie; Xu, Tao; Lu, Junpeng Research, Vol. 2019 https://doi.org/10.34133/2019/4641739	journal	December 2019
Two-Dimensional-Material-Based Field-Effect Transistor Biosensor for Detecting COVID-19 Virus (SARS-CoV-2) Fathi-Hafshejani, Parvin; Azam, Nurul; Wang, Lu ACS Nano, Vol. 15, Issue 7 https://doi.org/10.1021/acsnano.1c01188	journal	June 2021
Quaternary 2D Transition Metal Dichalcogenides (TMDs) with Tunable Bandgap Susarla, Sandhya; Kutana, Alex; Hachtel, Jordan A. Advanced Materials, Vol. 29, Issue 35 https://doi.org/10.1002/adma.201702457	journal	July 2017
Laser Thinning and Patterning of MoS2 with Layer-by-Layer Precision Hu, Lili; Shan, Xinyan; Wu, Yanling Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/s41598-017-15350-4	journal	November 2017
Thermal behavior of materials in laser-assisted extreme manufacturing: Raman-based novel characterization Wang, Ridong; Xu, Shen; Yue, Yanan International Journal of Extreme Manufacturing, Vol. 2, Issue 3 https://doi.org/10.1088/2631-7990/aba17c	journal	August 2020
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
Bandgap engineering of two-dimensional semiconductor materials Chaves, A.; Azadani, J. G.; Alsalman, Hussain npj 2D Materials and Applications, Vol. 4, Issue 1 https://doi.org/10.1038/s41699-020-00162-4	journal	August 2020
Atomistic Positioning of Defects in Helium Ion Treated Single-Layer MoS ₂ Mitterreiter, Elmar; Schuler, Bruno; Cochrane, Katherine A. Nano Letters, Vol. 20, Issue 6 https://doi.org/10.1021/acs.nanolett.0c01222	journal	May 2020
Gas Molecules on Defective and Nonmetal-Doped MoS₂ Monolayers Linghu, Yaoyao; Wu, Chao The Journal of Physical Chemistry C, Vol. 124, Issue 2 https://doi.org/10.1021/acs.jpcc.9b10450	journal	December 2019
Accelerated synthesis of atomically-thin 2D quantum materials by a novel laser-assisted synthesis technique Azam, Nurul; Ahmadi, Zabihollah; Yakupoglu, Baha 2D Materials, Vol. 7, Issue 1 https://doi.org/10.1088/2053-1583/ab53f7	journal	November 2019
Single-Atom Vacancy Doping in Two-Dimensional Transition Metal Dichalcogenides Zhang, Xiankun; Gao, Li; Yu, Huihui Accounts of Materials Research, Vol. 2, Issue 8 https://doi.org/10.1021/accountsmr.1c00097	journal	July 2021
Air-Stable n-Doping of WSe ₂ by Anion Vacancy Formation with Mild Plasma Treatment Tosun, Mahmut; Chan, Leslie; Amani, Matin ACS Nano, Vol. 10, Issue 7 https://doi.org/10.1021/acsnano.6b02521	journal	June 2016
Tailoring Vacancies Far Beyond Intrinsic Levels Changes the Carrier Type and Optical Response in Monolayer MoSe _{2− x} Crystals Mahjouri-Samani, Masoud; Liang, Liangbo; Oyedele, Akinola Nano Letters, Vol. 16, Issue 8 https://doi.org/10.1021/acs.nanolett.6b02263	journal	July 2016
Molecular assembly on two-dimensional materials Kumar, Avijit; Banerjee, Kaustuv; Liljeroth, Peter Nanotechnology, Vol. 28, Issue 8 https://doi.org/10.1088/1361-6528/aa564f	journal	January 2017
Phonons in single-layer and few-layer MoS $_{2}$ and WS $_{2}$ Molina-Sánchez, A.; Wirtz, L. Physical Review B, Vol. 84, Issue 15 https://doi.org/10.1103/PhysRevB.84.155413	journal	October 2011
Filling Exciton Trap-States in Two-Dimensional Tungsten Disulfide (WS2) and Diselenide (WSe2) Monolayers Ezgi Eroglu, Zeynep; Contreras, Dillon; Bahrami, Pouya Nanomaterials, Vol. 11, Issue 3 https://doi.org/10.3390/nano11030770	journal	March 2021
Prospects and challenges of quantum emitters in 2D materials Azzam, Shaimaa I.; Parto, Kamyar; Moody, Galan Applied Physics Letters, Vol. 118, Issue 24 https://doi.org/10.1063/5.0054116	journal	June 2021
Defect-related dynamics of photoexcited carriers in 2D transition metal dichalcogenides Gao, Lei; Hu, Zhenliang; Lu, Junpeng Physical Chemistry Chemical Physics, Vol. 23, Issue 14 https://doi.org/10.1039/D1CP00006C	journal	January 2021
Self-limiting laser crystallization and direct writing of 2D materials Ahmadi, Zabihollah; Yakupoglu, Baha; Azam, Nurul International Journal of Extreme Manufacturing, Vol. 1, Issue 1 https://doi.org/10.1088/2631-7990/ab0edc	journal	April 2019
Control of Radiation Damage in MoS ₂ by Graphene Encapsulation Zan, Recep; Ramasse, Quentin M.; Jalil, Rashid ACS Nano, Vol. 7, Issue 11 https://doi.org/10.1021/nn4044035	journal	October 2013
Unveiling Defect-Related Raman Mode of Monolayer WS₂ via Tip-Enhanced Resonance Raman Scattering Lee, Chanwoo; Jeong, Byeong Geun; Yun, Seok Joon ACS Nano, Vol. 12, Issue 10 https://doi.org/10.1021/acsnano.8b04265	journal	August 2018
Photoluminescence emission and Raman response of monolayer MoS_2, MoSe_2, and WSe_2 Tonndorf, Philipp; Schmidt, Robert; Böttger, Philipp Optics Express, Vol. 21, Issue 4 https://doi.org/10.1364/OE.21.004908	journal	January 2013
Direct observation of the transition from indirect to direct bandgap in atomically thin epitaxial MoSe2 Zhang, Yi; Chang, Tay-Rong; Zhou, Bo Nature Nanotechnology, Vol. 9, Issue 2 https://doi.org/10.1038/nnano.2013.277	journal	December 2013
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
In-depth characterization of stacking faults forming during the growth of Transition-Metal Di-Chalcogenides (TMDCs) by ambient pressure-CVD Konar, Rajashree; Tamari, Rimon; Teblum, Eti Materials Characterization, Vol. 184 https://doi.org/10.1016/j.matchar.2021.111666	journal	February 2022
Monolayer 2D quantum materials subjected to gamma irradiation in high-vacuum for nuclear and space applications Elafandi, Salah; Christiansen, Robert; Azam, Nurul Applied Physics Letters, Vol. 116, Issue 21 https://doi.org/10.1063/5.0006919	journal	May 2020
Electronics and optoelectronics of two-dimensional transition metal dichalcogenides Wang, Qing Hua; Kalantar-Zadeh, Kourosh; Kis, Andras Nature Nanotechnology, Vol. 7, Issue 11, p. 699-712 https://doi.org/10.1038/nnano.2012.193	journal	November 2012
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
Atomic structure of defects and dopants in 2D layered transition metal dichalcogenides Wang, Shanshan; Robertson, Alex; Warner, Jamie H. Chemical Society Reviews, Vol. 47, Issue 17 https://doi.org/10.1039/C8CS00236C	journal	January 2018
Defect Engineering in MoSe ₂ for the Hydrogen Evolution Reaction: From Point Defects to Edges Shu, Haibo; Zhou, Dong; Li, Feng ACS Applied Materials & Interfaces, Vol. 9, Issue 49 https://doi.org/10.1021/acsami.7b12478	journal	November 2017
Probing the Nature of Defects in Graphene by Raman Spectroscopy Eckmann, Axel; Felten, Alexandre; Mishchenko, Artem Nano Letters, Vol. 12, Issue 8 https://doi.org/10.1021/nl300901a	journal	July 2012
Ultrafast dynamics of exciton formation and decay in two-dimensional tungsten disulfide (2D-WS₂) monolayers Eroglu, Zeynep Ezgi; Comegys, Olivia; Quintanar, Leo S. Physical Chemistry Chemical Physics, Vol. 22, Issue 30 https://doi.org/10.1039/D0CP03220D	journal	January 2020
Neutral and defect-induced exciton annihilation in defective monolayer WS ₂ Liu, Huan; Wang, Chong; Liu, Dameng Nanoscale, Vol. 11, Issue 16 https://doi.org/10.1039/C9NR00967A	journal	January 2019
Defect Functionalization of MoS₂ nanostructures as toxic gas sensors: A review Ramanathan, A. A. IOP Conference Series: Materials Science and Engineering, Vol. 305 https://doi.org/10.1088/1757-899X/305/1/012001	journal	February 2018
Interface Thermal Resistance between Monolayer WSe ₂ and SiO ₂ : Raman Probing with Consideration of Optical–Acoustic Phonon Nonequilibrium Hunter, Nicholas; Azam, Nurul; Zobeiri, Hamidreza Advanced Materials Interfaces, Vol. 9, Issue 7 https://doi.org/10.1002/admi.202102059	journal	January 2022
A roadmap for graphene Novoselov, K. S.; Fal′ko, V. I.; Colombo, L. Nature, Vol. 490, Issue 7419 https://doi.org/10.1038/nature11458	journal	October 2012
Defect-Induced in Situ Atomic Doping in Transition Metal Dichalcogenides via Liquid-Phase Synthesis toward Efficient Electrochemical Activity Lee, Junghyun; Heo, Jungwoo; Lim, Hyeong Yong ACS Nano, Vol. 14, Issue 12 https://doi.org/10.1021/acsnano.0c06783	journal	December 2020
Laser synthesis and functionalization of nanostructures Grigoropoulos, Costas P. International Journal of Extreme Manufacturing, Vol. 1, Issue 1 https://doi.org/10.1088/2631-7990/ab0eca	journal	April 2019
Resonant Raman and Exciton Coupling in High-Quality Single Crystals of Atomically Thin Molybdenum Diselenide Grown by Vapor-Phase Chalcogenization Bilgin, Ismail; Raeliarijaona, Aldo S.; Lucking, Michael C. ACS Nano, Vol. 12, Issue 1 https://doi.org/10.1021/acsnano.7b07933	journal	January 2018
Thermoelectric Response of Bulk and Monolayer MoSe ₂ and WSe ₂ Kumar, S.; Schwingenschlögl, U. Chemistry of Materials, Vol. 27, Issue 4 https://doi.org/10.1021/cm504244b	journal	February 2015
Photoexcitation Dynamics and Long‐Lived Excitons in Strain‐Engineered Transition Metal Dichalcogenides Mondal, Navendu; Azam, Nurul; Gartstein, Yuri N. Advanced Materials, Vol. 34, Issue 23 https://doi.org/10.1002/adma.202110568	journal	April 2022
Influence of defect density on the gas sensing properties of multi-layered graphene grown by chemical vapor deposition Ricciardella, Filiberto; Vollebregt, Sten; Tilmann, Rita Carbon Trends, Vol. 3 https://doi.org/10.1016/j.cartre.2021.100024	journal	April 2021
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
Directing Assembly and Disassembly of 2D MoS 2 Nanosheets with DNA for Drug Delivery Li, Bang Lin; Setyawati, Magdiel I.; Chen, Linye ACS Applied Materials & Interfaces, Vol. 9, Issue 18 https://doi.org/10.1021/acsami.7b02529	journal	April 2017
New First Order Raman-active Modes in Few Layered Transition Metal Dichalcogenides Terrones, H.; Corro, E. Del; Feng, S. Scientific Reports, Vol. 4, Issue 1 https://doi.org/10.1038/srep04215	journal	February 2014
Atomic Vacancy Control and Elemental Substitution in a Monolayer Molybdenum Disulfide for High Performance Optoelectronic Device Arrays Chee, Sang‐Soo; Lee, Won‐June; Jo, Yong‐Ryun Advanced Functional Materials, Vol. 30, Issue 11 https://doi.org/10.1002/adfm.201908147	journal	January 2020
Atomic Healing of Defects in Transition Metal Dichalcogenides Lu, Junpeng; Carvalho, Alexandra; Chan, Xinhui Kim Nano Letters, Vol. 15, Issue 5 https://doi.org/10.1021/acs.nanolett.5b00952	journal	April 2015
Microsecond Valley Lifetime of Defect-Bound Excitons in Monolayer WSe 2 Moody, Galan; Tran, Kha; Lu, Xiaobo Physical Review Letters, Vol. 121, Issue 5 https://doi.org/10.1103/PhysRevLett.121.057403	journal	August 2018

Similar Records

Suppression of Defects and Deep Levels Using Isoelectronic Tungsten Substitution in Monolayer MoSe₂

Journal Article · Thu May 18 00:00:00 EDT 2017 · Advanced Functional Materials (Online) · OSTI ID:1883659

Li, Xufan; Puretzky, Alexander A.; Sang, Xiahan; +12 more

Isoelectronic tungsten doping in monolayer MoSe₂ for carrier type modulation

Journal Article · Wed Jul 06 00:00:00 EDT 2016 · Advanced Materials · OSTI ID:1883659

Li, Xufan; Lin, Ming -Wei; Basile, Leonardo; +12 more

Edge-Mediated Annihilation of Vacancy Clusters in Monolayer Molybdenum Diselenide (MoSe₂) under Electron Beam Irradiation

Journal Article · Tue Nov 16 00:00:00 EST 2021 · Small · OSTI ID:1883659

Zhang, Xu; Zhang, Xiang; Ajayan, Pulickel M.; +2 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
laser-assisted synthesis
2D materials
TMDCs
defect engineering
vacancy tuning

Title: Laser-Assisted Synthesis of Monolayer 2D MoSe2 Crystals with Tunable Vacancy Concentrations: Implications for Gas and Biosensing

Citation Formats

References (68)

Similar Records

Related Subjects

Title: Laser-Assisted Synthesis of Monolayer 2D MoSe₂ Crystals with Tunable Vacancy Concentrations: Implications for Gas and Biosensing