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Title: Electronic Coupling in Metallophthalocyanine–Transition Metal Dichalcogenide Mixed-Dimensional Heterojunctions

Abstract

Mixed-dimensional heterojunctions, such as zero-dimensional (0D) organic molecules deposited on two-dimensional (2D) transition metal dichalcogenides (TMDCs), often exhibit interfacial effects that enhance the properties of the individual constituent layers. Here we report a systematic study of interfacial charge transfer in metallophthalocyanine (MPc) – MoS2 heterojunctions using optical absorption and Raman spectroscopy to elucidate M core (M = first row transition metal), MoS2 layer number, and excitation wavelength effects. Observed phenomena include the emergence of heterojunctionspecific optical absorption transitions and strong Raman enhancement that depends on the M identity. In addition, the Raman enhancement is tunable by excitation laser wavelength and MoS2 layer number, ultimately reaching a maximum enhancement factor of 30x relative to SiO2 substrates. These experimental results, combined with density functional theory (DFT) calculations, indicate strong coupling between nonfrontier MPc orbitals and the MoS2 band structure as well as charge transfer across the heterojunction interface that varies as a function of the MPc electronic structure.

Authors:
 [1];  [2]; ORCiD logo [3];  [2];  [2]; ORCiD logo [4]; ORCiD logo [5];  [6]; ORCiD logo [5]
+ Show Author Affiliations
  1. Northwestern Univ., Evanston, IL (United States); Center for Light Energy Activated Redox Processes, Evanston, IL (United States)
  2. Northwestern Univ., Evanston, IL (United States)
  3. Northwestern Univ., Evanston, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials; Northwestern Argonne Inst. for Science and Engineering, Evanston, IL (United States)
  5. Northwestern Univ., Evanston, IL (United States); Center for Light Energy Activated Redox Processes, Evanston, IL (United States)
  6. Northwestern Univ., Evanston, IL (United States); Northwestern Argonne Inst. for Science and Engineering, Evanston, IL (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Light Energy Activated Redox Processes (LEAP); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF) - Directorate for Mathematical and Physical Sciences Division of Materials Research (MPS-DMR); National Institute of Standards and Technology (NIST) - Center for Hierarchical Materials Design (CHiMaD); USDOE Office of Science - Office of Basic Energy Sciences - Scientific User Facilities Division; USDOE Office of Science (SC), Basic Energy Sciences (BES); U.S. Department of Defense (DOD); W.M. Keck Foundation
OSTI Identifier:
1558628
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 13; Journal Issue: 4; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; charge transfer; heterojunction; metallophthalocyanine; phthalocyanine; transition metal dichalcogenide

Citation Formats

Amsterdam, Samuel H., Stanev, Teodor K., Zhou, Qunfei, Lou, Alexander J. -T., Bergeron, Hadallia, Darancet, Pierre, Hersam, Mark C., Stern, Nathaniel P., and Marks, Tobin J. Electronic Coupling in Metallophthalocyanine–Transition Metal Dichalcogenide Mixed-Dimensional Heterojunctions. United States: N. p., 2019. Web. doi:10.1021/acsnano.8b09166.
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Amsterdam, Samuel H., Stanev, Teodor K., Zhou, Qunfei, Lou, Alexander J. -T., Bergeron, Hadallia, Darancet, Pierre, Hersam, Mark C., Stern, Nathaniel P., & Marks, Tobin J. Electronic Coupling in Metallophthalocyanine–Transition Metal Dichalcogenide Mixed-Dimensional Heterojunctions. United States. https://doi.org/10.1021/acsnano.8b09166
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Amsterdam, Samuel H., Stanev, Teodor K., Zhou, Qunfei, Lou, Alexander J. -T., Bergeron, Hadallia, Darancet, Pierre, Hersam, Mark C., Stern, Nathaniel P., and Marks, Tobin J. Fri . "Electronic Coupling in Metallophthalocyanine–Transition Metal Dichalcogenide Mixed-Dimensional Heterojunctions". United States. https://doi.org/10.1021/acsnano.8b09166. https://www.osti.gov/servlets/purl/1558628.
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@article{osti_1558628,
title = {Electronic Coupling in Metallophthalocyanine–Transition Metal Dichalcogenide Mixed-Dimensional Heterojunctions},
author = {Amsterdam, Samuel H. and Stanev, Teodor K. and Zhou, Qunfei and Lou, Alexander J. -T. and Bergeron, Hadallia and Darancet, Pierre and Hersam, Mark C. and Stern, Nathaniel P. and Marks, Tobin J.},
abstractNote = {Mixed-dimensional heterojunctions, such as zero-dimensional (0D) organic molecules deposited on two-dimensional (2D) transition metal dichalcogenides (TMDCs), often exhibit interfacial effects that enhance the properties of the individual constituent layers. Here we report a systematic study of interfacial charge transfer in metallophthalocyanine (MPc) – MoS2 heterojunctions using optical absorption and Raman spectroscopy to elucidate M core (M = first row transition metal), MoS2 layer number, and excitation wavelength effects. Observed phenomena include the emergence of heterojunctionspecific optical absorption transitions and strong Raman enhancement that depends on the M identity. In addition, the Raman enhancement is tunable by excitation laser wavelength and MoS2 layer number, ultimately reaching a maximum enhancement factor of 30x relative to SiO2 substrates. These experimental results, combined with density functional theory (DFT) calculations, indicate strong coupling between nonfrontier MPc orbitals and the MoS2 band structure as well as charge transfer across the heterojunction interface that varies as a function of the MPc electronic structure.},
doi = {10.1021/acsnano.8b09166},
journal = {ACS Nano},
number = 4,
volume = 13,
place = {United States},
year = {Fri Mar 08 00:00:00 EST 2019},
month = {Fri Mar 08 00:00:00 EST 2019}
}
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https://doi.org/10.1021/acsnano.8b09166
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