Single Nanoflake Photoelectrochemistry Reveals Intrananoflake Doping Heterogeneity That Explains Ensemble-Level Photoelectrochemical Behavior

Erdewyk, Michael Van; Sambur, Justin B.

doi:10.1021/acsami.1c14928

Title: Single Nanoflake Photoelectrochemistry Reveals Intrananoflake Doping Heterogeneity That Explains Ensemble-Level Photoelectrochemical Behavior

Journal Article · Mon Nov 01 00:00:00 EDT 2021 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.1c14928· OSTI ID:1830754

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Colorado State Univ., Fort Collins, CO (United States)

Transition metal dichalcogenide (TMD) nanoflake thin films are attractive electrode materials for photoelectrochemical (PEC) solar energy conversion and sensing applications, but their photocurrent quantum yields are generally lower than those of bulk TMD electrodes. The poor PEC performance has been primarily attributed to enhanced charge carrier recombination at exposed defect and edge sites introduced by the exfoliation process. In this work, a single nanoflake PEC approach reveals how an alternative effect, doping heterogeneity, limits ensemble-level PEC performance. Photocurrent mapping and local photocurrent–potential (i–E) measurements of MoS₂ nanoflakes exfoliated from naturally occurring bulk crystals revealed the presence of n- and ptype domains within the same nanoflake. Interestingly, the n- and p-type domains in the natural MoS₂ nanoflakes were equally efficient for iodide oxidation and tri-iodide reduction (IQE values exceed 80%). At the single domain-level, the natural MoS₂ nanoflakes were nearly as efficient as nanoflakes exfoliated from synthetic n-type MoS₂ crystals. Single domain-level i–E measurements explain why natural MoS₂ nanoflakes exhibit an n-type to p-type photocurrent switching effect in ensemble-level measurements: the n- and p-type diode currents from individual domains oppose each other upon illuminating the entire nanoflake, resulting in zero photocurrent at the switching potential. The doping heterogeneity effect is likely due to nonideal stoichiometry, where p-type domains are S-rich according to XPS measurements. Although this doping heterogeneity effect limits photoanode or photocathode performance, these findings open the possibility to synthesize efficient TMD nanoflake photocatalysts with well-defined lateral p- and n-type domains for enhanced charge separation.

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Research Organization:: Colorado State Univ., Fort Collins, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0021189

OSTI ID:: 1830754

Journal Information:: ACS Applied Materials and Interfaces, Vol. 14, Issue 20; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (64)

Single-Nanoflake Photo-Electrochemistry Reveals Champion and Spectator Flakes in Exfoliated MoSe ₂ Films Todt, Michael A.; Isenberg, Allan E.; Nanayakkara, Sanjini U. The Journal of Physical Chemistry C, Vol. 122, Issue 12 https://doi.org/10.1021/acs.jpcc.7b12715	journal	March 2018
Efficiency losses from carrier‐type inhomogeneity in tungsten diselenide photoelectrodes Menezes, S.; Schneemeyer, L. F.; Lewerenz, H. J. Applied Physics Letters, Vol. 38, Issue 11 https://doi.org/10.1063/1.92193	journal	June 1981
Origin of $n$ -type conductivity of monolayer ${MoS}_{2}$ Singh, Akash; Singh, Abhishek Kumar Physical Review B, Vol. 99, Issue 12 https://doi.org/10.1103/PhysRevB.99.121201	journal	March 2019
MoS2 impurities: Chemical identification and spatial resolution of bismuth impurities in geological material Sales, Maria Gabriela; Herweyer, Lucas; Opila, Elizabeth Applied Surface Science, Vol. 508 https://doi.org/10.1016/j.apsusc.2020.145256	journal	April 2020
Removing Defects in WSe ₂ via Surface Oxidation and Etching to Improve Solar Conversion Performance Shearer, Melinda J.; Li, Wenjie; Foster, Jayson G. ACS Energy Letters, Vol. 4, Issue 1 https://doi.org/10.1021/acsenergylett.8b01922	journal	December 2018
Semiconducting Properties of Single Crystals of n ‐ and p ‐Type Tungsten Diselenide (WSe ₂ ) Upadhyayula, L. C.; Loferski, J. J.; Wold, A. Journal of Applied Physics, Vol. 39, Issue 10 https://doi.org/10.1063/1.1655829	journal	September 1968
Performance of Synthetical n-MoSe[sub 2] in Electrochemical Solar Cells Gobrecht, J. Journal of The Electrochemical Society, Vol. 125, Issue 12 https://doi.org/10.1149/1.2131370	journal	January 1978
The Role of Surface Orientation in the Photoelectrochemical Behavior of Layer Type d-Band Semiconductors Kautek, W.; Gerischer, H.; Tributsch, H. Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 83, Issue 10 https://doi.org/10.1002/bbpc.19790831010	journal	October 1979
Impact of intrinsic atomic defects on the electronic structure of MoS ₂ monolayers Kc, Santosh; Longo, Roberto C.; Addou, Rafik Nanotechnology, Vol. 25, Issue 37 https://doi.org/10.1088/0957-4484/25/37/375703	journal	August 2014
Electrochemical Solar Cell Based on the d-Band Semiconductor Tungsten-Diselenide Gobrecht, J.; Gerischer, H.; Tributsch, H. Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 82, Issue 12 https://doi.org/10.1002/bbpc.19780821212	journal	December 1978
Impurities and Electronic Property Variations of Natural MoS ₂ Crystal Surfaces Addou, Rafik; McDonnell, Stephen; Barrera, Diego ACS Nano, Vol. 9, Issue 9 https://doi.org/10.1021/acsnano.5b03309	journal	August 2015
Passivation of recombination centers in n ‐WSe ₂ yields high efficiency (>14%) photoelectrochemical cell Tenne, R.; Wold, A. Applied Physics Letters, Vol. 47, Issue 7 https://doi.org/10.1063/1.96066	journal	October 1985
Relationship between surface morphology and solar conversion efficiency of tungsten diselenide photoanodes Lewerenz, H. J.; Heller, A.; DiSalvo, F. J. Journal of the American Chemical Society, Vol. 102, Issue 6 https://doi.org/10.1021/ja00526a019	journal	March 1980
Evaluation and reduction of efficiency losses at tungsten diselenide photoanodes Parkinson, Bruce A.; Furtak, Thomas E.; Canfield, Duane Faraday Discussions of the Chemical Society, Vol. 70 https://doi.org/10.1039/dc9807000233	journal	January 1980
Deterministic transfer of two-dimensional materials by all-dry viscoelastic stamping Castellanos-Gomez, Andres; Buscema, Michele; Molenaar, Rianda 2D Materials, Vol. 1, Issue 1 https://doi.org/10.1088/2053-1583/1/1/011002	journal	April 2014
Improvement of energy conversion efficiency by specific chemical treatments of molybdenum selenide (n-MoSe2) and tungsten selenide (n-WSe2) photoanodes Canfield, D.; Parkinson, B. A. Journal of the American Chemical Society, Vol. 103, Issue 5 https://doi.org/10.1021/ja00395a076	journal	March 1981
van der Waals Layered Materials: Opportunities and Challenges Duong, Dinh Loc; Yun, Seok Joon; Lee, Young Hee ACS Nano, Vol. 11, Issue 12 https://doi.org/10.1021/acsnano.7b07436	journal	October 2016
Semiconductor Electrodes Fan, Fu-Ren F. Journal of The Electrochemical Society, Vol. 128, Issue 5 https://doi.org/10.1149/1.2127580	journal	January 1981
Structural Features Dictate the Photoelectrochemical Activities of Two-Dimensional MoSe ₂ and WSe ₂ Nanostructures Tóth, Péter S.; Szabó, Gábor; Janáky, Csaba The Journal of Physical Chemistry C, Vol. 125, Issue 14 https://doi.org/10.1021/acs.jpcc.1c01265	journal	March 2021
Locally Engineering and Interrogating the Photoelectrochemical Behavior of Defects in Transition Metal Dichalcogenides Hill, Joshua W.; Fu, Zhuangen; Tian, Jifa The Journal of Physical Chemistry C, Vol. 124, Issue 31 https://doi.org/10.1021/acs.jpcc.0c05235	journal	July 2020
Directly visualizing carrier transport and recombination at individual defects within 2D semiconductors Hill, Joshua W.; Hill, Caleb M. Chemical Science, Vol. 12, Issue 14 https://doi.org/10.1039/D0SC07033E	journal	January 2021
Ambipolar MoS ₂ Thin Flake Transistors Zhang, Yijin; Ye, Jianting; Matsuhashi, Yusuke Nano Letters, Vol. 12, Issue 3 https://doi.org/10.1021/nl2021575	journal	February 2012
Disassembling 2D van der Waals crystals into macroscopic monolayers and reassembling into artificial lattices Liu, Fang; Wu, Wenjing; Bai, Yusong Science, Vol. 367, Issue 6480 https://doi.org/10.1126/science.aba1416	journal	February 2020
Efficient and stable photoelectrochemical cells constructed with WSe2 and MoSe2 photoanodes Kline, G.; Kam, K.; Canfield, D. Solar Energy Materials, Vol. 4, Issue 3 https://doi.org/10.1016/0165-1633(81)90068-X	journal	March 1981
Scanning light‐spot analysis of the carrier collection in liquid‐junction solar energy converters Furtak, T. E.; Canfield, D. C.; Parkinson, B. A. Journal of Applied Physics, Vol. 51, Issue 11 https://doi.org/10.1063/1.327524	journal	November 1980
Imaging the Anisotropic Reactivity of a Tungsten Diselenide Photocathode Eisenberg, David ChemElectroChem, Vol. 2, Issue 9 https://doi.org/10.1002/celc.201500103	journal	June 2015
Self-assembled 2D WSe2 thin films for photoelectrochemical hydrogen production Yu, Xiaoyun; Prévot, Mathieu S.; Guijarro, Néstor Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8596	journal	July 2015
Further studies of the photoelectrochemical properties of the group VI transition metal dichalcogenides Kline, Gary; Kam, Kam Keung; Ziegler, Ruth Solar Energy Materials, Vol. 6, Issue 3 https://doi.org/10.1016/0165-1633(82)90039-9	journal	March 1982
Native defects in bulk and monolayer ${MoS}_{2}$ from first principles Komsa, Hannu-Pekka; Krasheninnikov, Arkady V. Physical Review B, Vol. 91, Issue 12 https://doi.org/10.1103/PhysRevB.91.125304	journal	March 2015
A scanning probe investigation of the role of surface motifs in the behavior of p-WSe ₂ photocathodes Velazquez, Jesus M.; John, Jimmy; Esposito, Daniel V. Energy & Environmental Science, Vol. 9, Issue 1 https://doi.org/10.1039/C5EE02530C	journal	January 2016
Digital Imaging of the Effect of Photoetching on the Photoresponse of n-Type Tungsten Diselenide and Molybdenum Diselenide Single Crystal Electrodes Salvador, P.; Chaparro, A. M.; Mir, A. The Journal of Physical Chemistry, Vol. 100, Issue 2 https://doi.org/10.1021/jp952001x	journal	January 1996
Identification of rhenium donors and sulfur vacancy acceptors in layered MoS ₂ bulk samples Brandão, F. D.; Ribeiro, G. M.; Vaz, P. H. Journal of Applied Physics, Vol. 119, Issue 23 https://doi.org/10.1063/1.4954017	journal	June 2016
Defect-Dominated Doping and Contact Resistance in MoS ₂ McDonnell, Stephen; Addou, Rafik; Buie, Creighton ACS Nano, Vol. 8, Issue 3 https://doi.org/10.1021/nn500044q	journal	February 2014
Photoelectrochemistry of WSe[sub 2] Electrodes Lewerenz, H. J. Journal of The Electrochemical Society, Vol. 131, Issue 1 https://doi.org/10.1149/1.2115467	journal	January 1984
Exfoliation of large-area transition metal chalcogenide single layers Magda, Gábor Zsolt; Pető, János; Dobrik, Gergely Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep14714	journal	October 2015
Hydrogen Evolution from Pt/Ru-Coated p-Type WSe ₂ Photocathodes McKone, James R.; Pieterick, Adam P.; Gray, Harry B. Journal of the American Chemical Society, Vol. 135, Issue 1 https://doi.org/10.1021/ja308581g	journal	December 2012
Defect Mitigation of Solution-Processed 2D WSe ₂ Nanoflakes for Solar-to-Hydrogen Conversion Yu, Xiaoyun; Guijarro, Néstor; Johnson, Melissa Nano Letters, Vol. 18, Issue 1 https://doi.org/10.1021/acs.nanolett.7b03948	journal	December 2017
Photoreactions at the n -type- ${WSe}_{2}$ –electrolyte interface: Study by electrolyte electroreflectance and photocurrent transient measurements Salvador, P.; Pujadas, M.; Campet, G. Physical Review B, Vol. 38, Issue 14 https://doi.org/10.1103/PhysRevB.38.9881	journal	November 1988
Bridging the Gap Between Bulk and Nanostructured Photoelectrodes: The Impact of Surface States on the Electrocatalytic and Photoelectrochemical Properties of MoS ₂ Chen, Zhebo; Forman, Arnold J.; Jaramillo, Thomas F. The Journal of Physical Chemistry C, Vol. 117, Issue 19 https://doi.org/10.1021/jp311375k	journal	May 2013
Unravelling the effect of sulfur vacancies on the electronic structure of the MoS ₂ crystal Zhang, Xixia; Wang, Shanpeng; Lee, Chao-Kuei Physical Chemistry Chemical Physics, Vol. 22, Issue 38 https://doi.org/10.1039/C9CP07004D	journal	January 2020
Semiconductor Electrodes: XLI . Improvement of Performance of Electrodes by Electrochemical Polymerization of o‐Phenylenediamine at Surface Imperfections White, Henry S.; Abruna, Hector D.; Bard, Allen J. Journal of The Electrochemical Society, Vol. 129, Issue 2 https://doi.org/10.1149/1.2123810	journal	February 1982
2D Nanomaterials for Photocatalytic Hydrogen Production Ganguly, Priyanka; Harb, Moussab; Cao, Zhen ACS Energy Letters, Vol. 4, Issue 7 https://doi.org/10.1021/acsenergylett.9b00940	journal	June 2019
Improved photoactivity of melt-grown group VI transition metal dichalcogenides Hofmann, W. K.; Lewerenz, H. J. Solar Energy Materials, Vol. 17, Issue 5 https://doi.org/10.1016/0165-1633(88)90018-4	journal	August 1988
Detailed photocurrent spectroscopy of the semiconducting group VIB transition metal dichalcogenides Kam, K. K.; Parkinson, B. A. The Journal of Physical Chemistry, Vol. 86, Issue 4 https://doi.org/10.1021/j100393a010	journal	February 1982
Solar Energy-Assisted Electrochemical Splitting of Water. Some Energetical, Kinetical and Catalytical Considerations Verified on MoS ₂ Layer Crystal Surfaces Tributsch, H. Zeitschrift für Naturforschung A, Vol. 32, Issue 9 https://doi.org/10.1515/zna-1977-0911	journal	September 1977
Progress of Large-Scale Synthesis and Electronic Device Application of Two-Dimensional Transition Metal Dichalcogenides Song, Xiongfei; Guo, Zhongxun; Zhang, Qiaochu Small, Vol. 13, Issue 35 https://doi.org/10.1002/smll.201700098	journal	July 2017
Photoelectrochemistry of Pristine Mono- and Few-Layer MoS ₂ Velický, Matěj; Bissett, Mark A.; Woods, Colin R. Nano Letters, Vol. 16, Issue 3 https://doi.org/10.1021/acs.nanolett.5b05317	journal	February 2016
Electrochemically Probing Exciton Transport in Monolayers of Two-Dimensional Semiconductors Tolbert, Chloe L.; Hill, Caleb Faraday Discussions https://doi.org/10.1039/D1FD00052G	journal	January 2021
Semiconductor Electrodes Fan, Fu-Ren F. Journal of The Electrochemical Society, Vol. 127, Issue 2 https://doi.org/10.1149/1.2129700	journal	January 1980
Role of Photogenerated Iodine on the Energy-Conversion Properties of MoSe ₂ Nanoflake Liquid Junction Photovoltaics Isenberg, Allan E.; Todt, Michael A.; Wang, Li ACS Applied Materials & Interfaces, Vol. 10, Issue 33 https://doi.org/10.1021/acsami.8b07617	journal	July 2018
Stability and electronic structures of native defects in single-layer ${MoS}_{2}$ Noh, Ji-Young; Kim, Hanchul; Kim, Yong-Sung Physical Review B, Vol. 89, Issue 20 https://doi.org/10.1103/PhysRevB.89.205417	journal	May 2014
Directly Mapping Photoelectrochemical Behavior within Individual Transition Metal Dichalcogenide Nanosheets Hill, Joshua W.; Hill, Caleb M. Nano Letters, Vol. 19, Issue 8 https://doi.org/10.1021/acs.nanolett.9b02336	journal	July 2019
Surface defects on n-MoSe2 electrodes used in photoelectrochemical solar cells Bicelli, L. Peraldo; Razzini, G. Surface Technology, Vol. 20, Issue 4 https://doi.org/10.1016/0376-4583(83)90116-4	journal	December 1983
Mott‐Schottky Plots and Flatband Potentials for Single Crystal Rutile Electrodes Cooper, G.; Turner, J. A.; Nozik, A. J. Journal of The Electrochemical Society, Vol. 129, Issue 9 https://doi.org/10.1149/1.2124334	journal	September 1982
Dynamics of cleaning, passivating and doping monolayer MoS ₂ by controlled laser irradiation Rao, Rahul; Carozo, Victor; Wang, Yuanxi 2D Materials, Vol. 6, Issue 4 https://doi.org/10.1088/2053-1583/ab33ab	journal	August 2019
Electrochemical solar cells based on layer-type transition metal compounds: Performance of electrode material Tributsch, Helmut Solar Energy Materials, Vol. 1, Issue 3-4 https://doi.org/10.1016/0165-1633(79)90044-3	journal	March 1979
The current‐voltage characteristics of semiconductor‐electrolyte junction photovoltaic cells Reichman, J. Applied Physics Letters, Vol. 36, Issue 7 https://doi.org/10.1063/1.91551	journal	April 1980
Toward Wafer‐Scale Production of 2D Transition Metal Chalcogenides Wang, Peijian; Yang, Deren; Pi, Xiaodong Advanced Electronic Materials, Vol. 7, Issue 8 https://doi.org/10.1002/aelm.202100278	journal	May 2021
Efficient Ultrathin Liquid Junction Photovoltaics Based on Transition Metal Dichalcogenides Wang, Li; Sambur, Justin B. Nano Letters, Vol. 19, Issue 5 https://doi.org/10.1021/acs.nanolett.9b00070	journal	March 2019
Giant Defect-Induced Effects on Nanoscale Charge Separation in Semiconductor Photocatalysts Chen, Ruotian; Pang, Shan; An, Hongyu Nano Letters, Vol. 19, Issue 1 https://doi.org/10.1021/acs.nanolett.8b04245	journal	December 2018
Toward Large-Area Solar Energy Conversion with Semiconducting 2D Transition Metal Dichalcogenides Yu, Xiaoyun; Sivula, Kevin ACS Energy Letters, Vol. 1, Issue 1 https://doi.org/10.1021/acsenergylett.6b00114	journal	June 2016
Roll-to-Roll Deposition of Semiconducting 2D Nanoflake Films of Transition Metal Dichalcogenides for Optoelectronic Applications Wells, Rebekah A.; Johnson, Hannah; Lhermitte, Charles R. ACS Applied Nano Materials, Vol. 2, Issue 12 https://doi.org/10.1021/acsanm.9b01774	journal	November 2019
Full Energy Spectra of Interface State Densities for n ‐ and p ‐type MoS ₂ Field‐Effect Transistors Fang, Nan; Toyoda, Satoshi; Taniguchi, Takashi Advanced Functional Materials, Vol. 29, Issue 49 https://doi.org/10.1002/adfm.201904465	journal	September 2019
High‐Resolution Electrochemical Mapping of the Hydrogen Evolution Reaction on Transition‐Metal Dichalcogenide Nanosheets Takahashi, Yasufumi; Kobayashi, Yu; Wang, Ziqian Angewandte Chemie International Edition, Vol. 59, Issue 9 https://doi.org/10.1002/anie.201912863	journal	January 2020

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Title: Single Nanoflake Photoelectrochemistry Reveals Intrananoflake Doping Heterogeneity That Explains Ensemble-Level Photoelectrochemical Behavior

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