Engineering Chemically Exfoliated Large-Area Two-Dimensional MoS2 Nanolayers with Porphyrins for Improved Light Harvesting

Hanyu Zhang, Jungwook Choi, Arjun Ramani, Damien Voiry, Sean N. Natoli, Manish Chhowalla, David R. McMillin, Jong Hyun Choi

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Molybdenum disulfide (MoS2) is a promising candidate for electronic and optoelectronic applications. However, its application in light harvesting has been limited in part due to crystal defects, often related to small crystallite sizes, which diminish charge separation and transfer. Here we demonstrate a surface-engineering strategy for 2D MoS2 to improve its photoelectrochemical properties. Chemically exfoliated large-area MoS2 thin films were interfaced with eight molecules from three porphyrin families: zinc(II)-, gallium(III)-, iron(III)-centered, and metal-free protoporphyrin IX (ZnPP, GaPP, FePP, H2PP); metal-free and zinc(II) tetra-(N-methyl-4-pyridyl)porphyrin (H2T4, ZnT4); and metal-free and zinc(II) tetraphenylporphyrin (H2TPP, ZnTPP). We found that the photocurrents from MoS2 films under visible-light illumination are strongly dependent on the interfacial molecules and that the photocurrent enhancement is closely correlated with the highest occupied molecular orbital (HOMO) levels of the porphyrins, which suppress the recombination of electron–hole pairs in the photoexcited MoS2 films. A maximum tenfold increase was observed for MoS2 functionalized with ZnPP compared with pristine MoS2 films, whereas ZnT4-functionalized MoS2 demonstrated small increases in photocurrent. The application of bias voltage on MoS2 films can further promote photocurrent enhancements and control current directions. Our results suggest a facile route to render 2D MoS2 films useful for potential high-performance light-harvesting applications.

Original languageEnglish
Pages (from-to)2854-2862
Number of pages9
JournalChemPhysChem
DOIs
Publication statusPublished - Sep 19 2016

Fingerprint

Porphyrins
porphyrins
Photocurrents
engineering
photocurrents
zinc
Metals
Zinc
metals
molybdenum disulfides
Gallium
Molecules
augmentation
Crystal defects
Electric current control
Molecular orbitals
polarization (charge separation)
Crystallite size
Bias voltage
crystal defects

Keywords

  • light harvesting
  • molybdenum disulfide
  • nanolayers
  • photocurrent
  • porphyrins

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Physical and Theoretical Chemistry

Cite this

Engineering Chemically Exfoliated Large-Area Two-Dimensional MoS2 Nanolayers with Porphyrins for Improved Light Harvesting. / Zhang, Hanyu; Choi, Jungwook; Ramani, Arjun; Voiry, Damien; Natoli, Sean N.; Chhowalla, Manish; McMillin, David R.; Choi, Jong Hyun.

In: ChemPhysChem, 19.09.2016, p. 2854-2862.

Research output: Contribution to journalArticle

Zhang, Hanyu ; Choi, Jungwook ; Ramani, Arjun ; Voiry, Damien ; Natoli, Sean N. ; Chhowalla, Manish ; McMillin, David R. ; Choi, Jong Hyun. / Engineering Chemically Exfoliated Large-Area Two-Dimensional MoS2 Nanolayers with Porphyrins for Improved Light Harvesting. In: ChemPhysChem. 2016 ; pp. 2854-2862.
@article{926e33a625f843b5a3a86b5b6035cd0e,
title = "Engineering Chemically Exfoliated Large-Area Two-Dimensional MoS2 Nanolayers with Porphyrins for Improved Light Harvesting",
abstract = "Molybdenum disulfide (MoS2) is a promising candidate for electronic and optoelectronic applications. However, its application in light harvesting has been limited in part due to crystal defects, often related to small crystallite sizes, which diminish charge separation and transfer. Here we demonstrate a surface-engineering strategy for 2D MoS2 to improve its photoelectrochemical properties. Chemically exfoliated large-area MoS2 thin films were interfaced with eight molecules from three porphyrin families: zinc(II)-, gallium(III)-, iron(III)-centered, and metal-free protoporphyrin IX (ZnPP, GaPP, FePP, H2PP); metal-free and zinc(II) tetra-(N-methyl-4-pyridyl)porphyrin (H2T4, ZnT4); and metal-free and zinc(II) tetraphenylporphyrin (H2TPP, ZnTPP). We found that the photocurrents from MoS2 films under visible-light illumination are strongly dependent on the interfacial molecules and that the photocurrent enhancement is closely correlated with the highest occupied molecular orbital (HOMO) levels of the porphyrins, which suppress the recombination of electron–hole pairs in the photoexcited MoS2 films. A maximum tenfold increase was observed for MoS2 functionalized with ZnPP compared with pristine MoS2 films, whereas ZnT4-functionalized MoS2 demonstrated small increases in photocurrent. The application of bias voltage on MoS2 films can further promote photocurrent enhancements and control current directions. Our results suggest a facile route to render 2D MoS2 films useful for potential high-performance light-harvesting applications.",
keywords = "light harvesting, molybdenum disulfide, nanolayers, photocurrent, porphyrins",
author = "Hanyu Zhang and Jungwook Choi and Arjun Ramani and Damien Voiry and Natoli, {Sean N.} and Manish Chhowalla and McMillin, {David R.} and Choi, {Jong Hyun}",
year = "2016",
month = "9",
day = "19",
doi = "10.1002/cphc.201600511",
language = "English",
pages = "2854--2862",
journal = "ChemPhysChem",
issn = "1439-4235",
publisher = "Wiley-VCH Verlag",

}

TY - JOUR

T1 - Engineering Chemically Exfoliated Large-Area Two-Dimensional MoS2 Nanolayers with Porphyrins for Improved Light Harvesting

AU - Zhang, Hanyu

AU - Choi, Jungwook

AU - Ramani, Arjun

AU - Voiry, Damien

AU - Natoli, Sean N.

AU - Chhowalla, Manish

AU - McMillin, David R.

AU - Choi, Jong Hyun

PY - 2016/9/19

Y1 - 2016/9/19

N2 - Molybdenum disulfide (MoS2) is a promising candidate for electronic and optoelectronic applications. However, its application in light harvesting has been limited in part due to crystal defects, often related to small crystallite sizes, which diminish charge separation and transfer. Here we demonstrate a surface-engineering strategy for 2D MoS2 to improve its photoelectrochemical properties. Chemically exfoliated large-area MoS2 thin films were interfaced with eight molecules from three porphyrin families: zinc(II)-, gallium(III)-, iron(III)-centered, and metal-free protoporphyrin IX (ZnPP, GaPP, FePP, H2PP); metal-free and zinc(II) tetra-(N-methyl-4-pyridyl)porphyrin (H2T4, ZnT4); and metal-free and zinc(II) tetraphenylporphyrin (H2TPP, ZnTPP). We found that the photocurrents from MoS2 films under visible-light illumination are strongly dependent on the interfacial molecules and that the photocurrent enhancement is closely correlated with the highest occupied molecular orbital (HOMO) levels of the porphyrins, which suppress the recombination of electron–hole pairs in the photoexcited MoS2 films. A maximum tenfold increase was observed for MoS2 functionalized with ZnPP compared with pristine MoS2 films, whereas ZnT4-functionalized MoS2 demonstrated small increases in photocurrent. The application of bias voltage on MoS2 films can further promote photocurrent enhancements and control current directions. Our results suggest a facile route to render 2D MoS2 films useful for potential high-performance light-harvesting applications.

AB - Molybdenum disulfide (MoS2) is a promising candidate for electronic and optoelectronic applications. However, its application in light harvesting has been limited in part due to crystal defects, often related to small crystallite sizes, which diminish charge separation and transfer. Here we demonstrate a surface-engineering strategy for 2D MoS2 to improve its photoelectrochemical properties. Chemically exfoliated large-area MoS2 thin films were interfaced with eight molecules from three porphyrin families: zinc(II)-, gallium(III)-, iron(III)-centered, and metal-free protoporphyrin IX (ZnPP, GaPP, FePP, H2PP); metal-free and zinc(II) tetra-(N-methyl-4-pyridyl)porphyrin (H2T4, ZnT4); and metal-free and zinc(II) tetraphenylporphyrin (H2TPP, ZnTPP). We found that the photocurrents from MoS2 films under visible-light illumination are strongly dependent on the interfacial molecules and that the photocurrent enhancement is closely correlated with the highest occupied molecular orbital (HOMO) levels of the porphyrins, which suppress the recombination of electron–hole pairs in the photoexcited MoS2 films. A maximum tenfold increase was observed for MoS2 functionalized with ZnPP compared with pristine MoS2 films, whereas ZnT4-functionalized MoS2 demonstrated small increases in photocurrent. The application of bias voltage on MoS2 films can further promote photocurrent enhancements and control current directions. Our results suggest a facile route to render 2D MoS2 films useful for potential high-performance light-harvesting applications.

KW - light harvesting

KW - molybdenum disulfide

KW - nanolayers

KW - photocurrent

KW - porphyrins

UR - http://www.scopus.com/inward/record.url?scp=84987732971&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84987732971&partnerID=8YFLogxK

U2 - 10.1002/cphc.201600511

DO - 10.1002/cphc.201600511

M3 - Article

SP - 2854

EP - 2862

JO - ChemPhysChem

JF - ChemPhysChem

SN - 1439-4235

ER -