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Title: Single-Nanoflake Photo-Electrochemistry Reveals Champion and Spectator Flakes in Exfoliated MoSe2 Films

Abstract

Semiconducting transition-metal dichalcogenide (TMD) nanoflake thin films are promising large-area electrodes for photo-electrochemical solar energy conversion applications. However, their energy conversion efficiencies are typically much lower than those of bulk electrodes. It is unclear to what extent this efficiency gap stems from differences among nanoflakes (e.g., area, thickness, and surface structural features). It is also unclear whether individual exfoliated nanoflakes can achieve energy conversion efficiencies similar to those of bulk crystals. Here, we use a single-nanoflake photo-electrochemical approach to show that there are both highly active and completely inactive nanoflakes within a film. For the exfoliated MoSe2 samples studied herein, 7% of nanoflakes are highly active champions, whose photocurrent efficiency exceeds that of the bulk crystal. However, 66% of nanoflakes are inactive spectators, which are mostly responsible for the overall lower photocurrent efficiency compared to the bulk crystal. The photocurrent collection efficiency increases with nanoflake area and decreases more at perimeter edges than at interior step edges. These observations, which are hidden in ensemble-level measurements, reveal the underlying performance issues of exfoliated TMD electrodes for photo-electrochemical energy conversion applications.

Authors:
 [1];  [1];  [2]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Colorado State Univ., Fort Collins, CO (United States)
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1435696
Report Number(s):
NREL/JA-5900-71132
Journal ID: ISSN 1932-7447; TRN: US1900084
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 12; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; transition-metal dichalcogenide; nanoflake thin films; photovoltiacs; solar energy conversion

Citation Formats

Todt, Michael A., Isenberg, Allan E., Nanayakkara, Sanjini U., Miller, Elisa M., and Sambur, Justin B. Single-Nanoflake Photo-Electrochemistry Reveals Champion and Spectator Flakes in Exfoliated MoSe2 Films. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.7b12715.
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Todt, Michael A., Isenberg, Allan E., Nanayakkara, Sanjini U., Miller, Elisa M., & Sambur, Justin B. Single-Nanoflake Photo-Electrochemistry Reveals Champion and Spectator Flakes in Exfoliated MoSe2 Films. United States. https://doi.org/10.1021/acs.jpcc.7b12715
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Todt, Michael A., Isenberg, Allan E., Nanayakkara, Sanjini U., Miller, Elisa M., and Sambur, Justin B. Tue . "Single-Nanoflake Photo-Electrochemistry Reveals Champion and Spectator Flakes in Exfoliated MoSe2 Films". United States. https://doi.org/10.1021/acs.jpcc.7b12715. https://www.osti.gov/servlets/purl/1435696.
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@article{osti_1435696,
title = {Single-Nanoflake Photo-Electrochemistry Reveals Champion and Spectator Flakes in Exfoliated MoSe2 Films},
author = {Todt, Michael A. and Isenberg, Allan E. and Nanayakkara, Sanjini U. and Miller, Elisa M. and Sambur, Justin B.},
abstractNote = {Semiconducting transition-metal dichalcogenide (TMD) nanoflake thin films are promising large-area electrodes for photo-electrochemical solar energy conversion applications. However, their energy conversion efficiencies are typically much lower than those of bulk electrodes. It is unclear to what extent this efficiency gap stems from differences among nanoflakes (e.g., area, thickness, and surface structural features). It is also unclear whether individual exfoliated nanoflakes can achieve energy conversion efficiencies similar to those of bulk crystals. Here, we use a single-nanoflake photo-electrochemical approach to show that there are both highly active and completely inactive nanoflakes within a film. For the exfoliated MoSe2 samples studied herein, 7% of nanoflakes are highly active champions, whose photocurrent efficiency exceeds that of the bulk crystal. However, 66% of nanoflakes are inactive spectators, which are mostly responsible for the overall lower photocurrent efficiency compared to the bulk crystal. The photocurrent collection efficiency increases with nanoflake area and decreases more at perimeter edges than at interior step edges. These observations, which are hidden in ensemble-level measurements, reveal the underlying performance issues of exfoliated TMD electrodes for photo-electrochemical energy conversion applications.},
doi = {10.1021/acs.jpcc.7b12715},
journal = {Journal of Physical Chemistry. C},
number = 12,
volume = 122,
place = {United States},
year = {Tue Mar 06 00:00:00 EST 2018},
month = {Tue Mar 06 00:00:00 EST 2018}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpcc.7b12715
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Cited by: 17 works
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Figures / Tables:

Figure 1 Figure 1: Photo-electrochemical characterization and microscopy of nanoflake and bulk MoSe2 electrodes. (a) Experimental setup for single-nanoflake photocurrent mapping in a three-electrode electro-chemical flow cell. The same cell was used for bulk crystal mapping. ctr = Pt wire counter electrode and ref = Ag/AgI wire reference electrode. (b) Current−potential curvesmore » of a 1.3 mm2 MoSe2 single crystal in 1 M NaI and 1 mM I2 electrolyte under dark (black line) and chopped 20 mW/cm2 532 nm laser illumination (red line). The light spot was larger than the crystal to illuminate the entire electrode surface. (c) Bright-field optical transmission image of the nanoflake-coated electrode immersed in 1 M NaI and 1 mM I2. (d) EQE map of the nanoflakes in (c) measured at +0.5 V vs Ag/AgI by scanning a 690 nm diameter 532 nm laser spot in 1 μm increments across the electrode surface. The illumination area and power were 0.37 μm2 and 3.0 μW, respectively, corresponding to a power density of 805 W/cm2. The red lines represent the nanoflake contour. (e) Photograph of the parent bulk MoSe2 crystal used for mechanical exfoliation. (f) EQE map of the bulk crystal in (e) measured at +0.5 V with a 4.94 μm diameter 532 nm laser spot in 7 μm increments across the electrode surface. The red line indicates the epoxy contour. The illumination area and power were 19.17 μm2 and 2.4 μW, corresponding to a power density of 12.5 W/cm2. The solution flow rate for both mapping experiments was 50 μL/min.« less
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Works referenced in this record:

Performance of Synthetical n-MoSe[sub 2] in Electrochemical Solar Cells
journal, January 1978

  • Gobrecht, J.
  • Journal of The Electrochemical Society, Vol. 125, Issue 12
  • DOI: 10.1149/1.2131370

Semiconductor Electrodes
journal, January 1980

  • Fan, Fu-Ren F.
  • Journal of The Electrochemical Society, Vol. 127, Issue 2
  • DOI: 10.1149/1.2129700

Relationship between surface morphology and solar conversion efficiency of tungsten diselenide photoanodes
journal, March 1980

  • Lewerenz, H. J.; Heller, A.; DiSalvo, F. J.
  • Journal of the American Chemical Society, Vol. 102, Issue 6
  • DOI: 10.1021/ja00526a019

Evaluation and reduction of efficiency losses at tungsten diselenide photoanodes
journal, January 1980

  • Parkinson, Bruce A.; Furtak, Thomas E.; Canfield, Duane
  • Faraday Discussions of the Chemical Society, Vol. 70
  • DOI: 10.1039/dc9807000233

Spontaneous Photoelectrolysis of HBr and HI
journal, January 1982

  • Levy-Clement, Claude
  • Journal of The Electrochemical Society, Vol. 129, Issue 8, p. 1701-1705
  • DOI: 10.1149/1.2124253

Electrochemical characterization of p-type semiconducting tungsten disulfide photocathodes: efficient photoreduction processes at semiconductor/liquid electrolyte interfaces
journal, April 1983

  • Baglio, Joseph A.; Calabrese, Gary S.; Harrison, D. Jed
  • Journal of the American Chemical Society, Vol. 105, Issue 8
  • DOI: 10.1021/ja00346a024

Tungsten disulfide: a novel hydrogen evolution catalyst for water decomposition
journal, April 1988

  • Sobczynski, Andrzej; Yildiz, Attila; Bard, Allen J.
  • The Journal of Physical Chemistry, Vol. 92, Issue 8
  • DOI: 10.1021/j100319a042

Hydrogen Evolution from Pt/Ru-Coated p-Type WSe 2 Photocathodes
journal, December 2012

  • McKone, James R.; Pieterick, Adam P.; Gray, Harry B.
  • Journal of the American Chemical Society, Vol. 135, Issue 1
  • DOI: 10.1021/ja308581g

Passivation of recombination centers in n ‐WSe 2 yields high efficiency (>14%) photoelectrochemical cell
journal, October 1985

  • Tenne, R.; Wold, A.
  • Applied Physics Letters, Vol. 47, Issue 7
  • DOI: 10.1063/1.96066

The high-efficiency (17.1%) WSe 2 photo-electrochemical solar cell
journal, June 1988

Materials Availability Expands the Opportunity for Large-Scale Photovoltaics Deployment
journal, March 2009

  • Wadia, Cyrus; Alivisatos, A. Paul; Kammen, Daniel M.
  • Environmental Science & Technology, Vol. 43, Issue 6
  • DOI: 10.1021/es8019534

Toward Large-Area Solar Energy Conversion with Semiconducting 2D Transition Metal Dichalcogenides
journal, June 2016

MoS 2 /WS 2 Heterojunction for Photoelectrochemical Water Oxidation
journal, July 2017

Self-assembled 2D WSe2 thin films for photoelectrochemical hydrogen production
journal, July 2015

  • Yu, Xiaoyun; Prévot, Mathieu S.; Guijarro, Néstor
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8596

Photogenerated Charge Harvesting and Recombination in Photocathodes of Solvent-Exfoliated WSe 2
journal, August 2017

Photoelectrochemistry of Pristine Mono- and Few-Layer MoS 2
journal, February 2016

The Role of Surface Defects in the Photooxidation of Iodide at n-MoSe2: Evidence for a Local "Autocatalytic" Effect
journal, April 1995

  • Chaparro, A. M.; Salvador, P.; Peter, L. M.
  • The Journal of Physical Chemistry, Vol. 99, Issue 17
  • DOI: 10.1021/j100017a059

Influence of crystal surface orientation on redox reactions at semiconducting MoS2
journal, June 1979

Photoelectrochemistry of WSe[sub 2] Electrodes
journal, January 1984

  • Lewerenz, H. J.
  • Journal of The Electrochemical Society, Vol. 131, Issue 1
  • DOI: 10.1149/1.2115467

Imaging the Anisotropic Reactivity of a Tungsten Diselenide Photocathode
journal, June 2015

Reliable Exfoliation of Large-Area High-Quality Flakes of Graphene and Other Two-Dimensional Materials
journal, September 2015

The scanning microscope for semiconductor characterization: photocurrent, photovoltage and electrolyte electroreflectance imaging at the n-MoSe2/I− interface
journal, March 1997

Photoinduced layer phenomenon caused by iodine formation in MoSe2: electrolyte (iodide) junctions
journal, January 1981

The application of chronocoulometry to the study of adsorption at the semiconductor/electrolyte interface
journal, July 1983

  • Turner, John A.; Parkinson, Bruce A.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 150, Issue 1-2
  • DOI: 10.1016/S0022-0728(83)80240-X

Critical analysis of electrical contacts to layered semiconductors for use in (photo)electrochemical studies
journal, September 1989

  • Etman, Mohamed; Neumann-Spallart, Michael
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 269, Issue 2
  • DOI: 10.1016/0022-0728(89)85148-4

Semiconductor Electrodes
journal, January 1981

  • Fan, Fu-Ren F.
  • Journal of The Electrochemical Society, Vol. 128, Issue 5
  • DOI: 10.1149/1.2127580

Electrochemical Solar Cell Based on the d-Band Semiconductor Tungsten-Diselenide
journal, December 1978

  • Gobrecht, J.; Gerischer, H.; Tributsch, H.
  • Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 82, Issue 12
  • DOI: 10.1002/bbpc.19780821212

Digital Imaging of the Effect of Photoetching on the Photoresponse of n-Type Tungsten Diselenide and Molybdenum Diselenide Single Crystal Electrodes
journal, January 1996

  • Salvador, P.; Chaparro, A. M.; Mir, A.
  • The Journal of Physical Chemistry, Vol. 100, Issue 2
  • DOI: 10.1021/jp952001x
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    • Wang, Li; Schmid, Merranda; Sambur, Justin B.
    • The Journal of Chemical Physics, Vol. 151, Issue 18
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