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Title: Photoresponse of Natural van der Waals Heterostructures

Abstract

Van der Waals heterostructures consisting of two-dimensional materials offer a platform to obtain materials by design and are very attractive owing to unique electronic states. Research on 2D van der Waals heterostructures (vdWH) has so far been focused on fabricating individually stacked atomically thin unary or binary crystals. Such systems include graphene, hexagonal boron nitride, and members of the transition metal dichalcogenide family. In this paper, we present our experimental study of the optoelectronic properties of a naturally occurring vdWH, known as franckeite, which is a complex layered crystal composed of lead, tin, antimony, iron, and sulfur. We present here that thin film franckeite (60 nm < d < 100 nm) behaves as a narrow band gap semiconductor demonstrating a wide-band photoresponse. We have observed the band-edge transition at ~1500 nm (~830 meV) and high external quantum efficiency (EQE ≈ 3%) at room temperature. Laser-power-resolved and temperature-resolved photocurrent measurements reveal that the photocarrier generation and recombination are dominated by continuously distributed trap states within the band gap. To understand wavelength-resolved photocurrent, we also calculated the optical absorption properties via density functional theory. Finally, we have shown that the device has a fast photoresponse with a rise time as fast asmore » ~1 ms. Finally, our study provides a fundamental understanding of the optoelectronic behavior in a complex naturally occurring vdWH, and may pave an avenue toward developing nanoscale optoelectronic devices with tailored properties.« less

Authors:
 [1];  [1];  [2];  [1];  [3]; ORCiD logo [2];  [3]; ORCiD logo [1]
  1. San Francisco State Univ., CA (United States)
  2. Univ. of Oklahoma, Norman, OK (United States)
  3. Stanford Univ., CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1487448
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 11; Journal Issue: 6; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; density functional theory; electronic transport; franckeite; photocurrent spectroscopy; photodetectors; van der Waals heterostructure

Citation Formats

Ray, Kyle, Yore, Alexander E., Mou, Tong, Jha, Sauraj, Smithe, Kirby K. H., Wang, Bin, Pop, Eric, and Newaz, A. K. M. Photoresponse of Natural van der Waals Heterostructures. United States: N. p., 2017. Web. https://doi.org/10.1021/acsnano.7b01918.
Ray, Kyle, Yore, Alexander E., Mou, Tong, Jha, Sauraj, Smithe, Kirby K. H., Wang, Bin, Pop, Eric, & Newaz, A. K. M. Photoresponse of Natural van der Waals Heterostructures. United States. https://doi.org/10.1021/acsnano.7b01918
Ray, Kyle, Yore, Alexander E., Mou, Tong, Jha, Sauraj, Smithe, Kirby K. H., Wang, Bin, Pop, Eric, and Newaz, A. K. M. Tue . "Photoresponse of Natural van der Waals Heterostructures". United States. https://doi.org/10.1021/acsnano.7b01918. https://www.osti.gov/servlets/purl/1487448.
@article{osti_1487448,
title = {Photoresponse of Natural van der Waals Heterostructures},
author = {Ray, Kyle and Yore, Alexander E. and Mou, Tong and Jha, Sauraj and Smithe, Kirby K. H. and Wang, Bin and Pop, Eric and Newaz, A. K. M.},
abstractNote = {Van der Waals heterostructures consisting of two-dimensional materials offer a platform to obtain materials by design and are very attractive owing to unique electronic states. Research on 2D van der Waals heterostructures (vdWH) has so far been focused on fabricating individually stacked atomically thin unary or binary crystals. Such systems include graphene, hexagonal boron nitride, and members of the transition metal dichalcogenide family. In this paper, we present our experimental study of the optoelectronic properties of a naturally occurring vdWH, known as franckeite, which is a complex layered crystal composed of lead, tin, antimony, iron, and sulfur. We present here that thin film franckeite (60 nm < d < 100 nm) behaves as a narrow band gap semiconductor demonstrating a wide-band photoresponse. We have observed the band-edge transition at ~1500 nm (~830 meV) and high external quantum efficiency (EQE ≈ 3%) at room temperature. Laser-power-resolved and temperature-resolved photocurrent measurements reveal that the photocarrier generation and recombination are dominated by continuously distributed trap states within the band gap. To understand wavelength-resolved photocurrent, we also calculated the optical absorption properties via density functional theory. Finally, we have shown that the device has a fast photoresponse with a rise time as fast as ~1 ms. Finally, our study provides a fundamental understanding of the optoelectronic behavior in a complex naturally occurring vdWH, and may pave an avenue toward developing nanoscale optoelectronic devices with tailored properties.},
doi = {10.1021/acsnano.7b01918},
journal = {ACS Nano},
number = 6,
volume = 11,
place = {United States},
year = {2017},
month = {5}
}

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Works referenced in this record:

Van der Waals heterostructures
journal, July 2013

  • Geim, A. K.; Grigorieva, I. V.
  • Nature, Vol. 499, Issue 7459, p. 419-425
  • DOI: 10.1038/nature12385

Van der Waals heterostructures and devices
journal, July 2016


2D materials and van der Waals heterostructures
journal, July 2016


Progress, Challenges, and Opportunities in Two-Dimensional Materials Beyond Graphene
journal, March 2013

  • Butler, Sheneve Z.; Hollen, Shawna M.; Cao, Linyou
  • ACS Nano, Vol. 7, Issue 4, p. 2898-2926
  • DOI: 10.1021/nn400280c

Franckeite as a naturally occurring van der Waals heterostructure
journal, February 2017

  • Molina-Mendoza, Aday J.; Giovanelli, Emerson; Paz, Wendel S.
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14409

Exfoliation of natural van der Waals heterostructures to a single unit cell thickness
journal, February 2017

  • Velický, Matěj; Toth, Peter S.; Rakowski, Alexander M.
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14410

The natural way
journal, March 2017


The crystal structure of franckeite, Pb21.7Sn9.3Fe4.0Sb8.1S56.9
journal, November 2011

  • Makovicky, E.; Petricek, V.; Dusek, M.
  • American Mineralogist, Vol. 96, Issue 11-12
  • DOI: 10.2138/am.2011.3814

Mutual Pb2+/Sn2+ substitution in sulfosalts
journal, July 1987


The absolute energy positions of conduction and valence bands of selected semiconducting minerals
journal, March 2000

  • Xu, Yong; Schoonen, Martin A. A.
  • American Mineralogist, Vol. 85, Issue 3-4
  • DOI: 10.2138/am-2000-0416

Optical band gaps of selected ternary sulfide minerals
journal, August 1998

  • Boldish, Steven I.; White, William B.
  • American Mineralogist, Vol. 83, Issue 7-8
  • DOI: 10.2138/am-1998-7-818

Structure and optical properties of PbS-SnS mixed crystal thin films
journal, May 2009

  • Unuchak, D. M.; Bente, K.; Kloess, G.
  • physica status solidi (c), Vol. 6, Issue 5
  • DOI: 10.1002/pssc.200881227

Cubic Form of Pb 2– x Sn x S 2 Stabilized through Size Reduction to the Nanoscale
journal, February 2012

  • Soriano, Ronald B.; Malliakas, Christos D.; Wu, Jinsong
  • Journal of the American Chemical Society, Vol. 134, Issue 6
  • DOI: 10.1021/ja211087q

Strong Phonon Scattering by Layer Structured PbSnS 2 in PbTe Based Thermoelectric Materials
journal, July 2012

  • He, Jiaqing; Girard, Steven N.; Zheng, Jin-Cheng
  • Advanced Materials, Vol. 24, Issue 32
  • DOI: 10.1002/adma.201201565

A transfer technique for high mobility graphene devices on commercially available hexagonal boron nitride
journal, December 2011

  • Zomer, P. J.; Dash, S. P.; Tombros, N.
  • Applied Physics Letters, Vol. 99, Issue 23
  • DOI: 10.1063/1.3665405

Raman scattering studies of SnS 2 and SnSe 2
journal, April 1977

  • Smith, A. J.; Meek, P. E.; Liang, W. Y.
  • Journal of Physics C: Solid State Physics, Vol. 10, Issue 8
  • DOI: 10.1088/0022-3719/10/8/035

Laser-induced transformation of stibnite (Sb2S3) and other structurally related salts
journal, September 2013


Raman spectra of SnS2 and SnSe2
journal, December 1976


Raman spectroscopy of PbS nanocrystalline semiconductors
journal, December 1998


Doping in semiconductors with variable activation energy
journal, January 1992

  • Tsang, W. T.; Schubert, E. F.; Cunningham, J. E.
  • Applied Physics Letters, Vol. 60, Issue 1
  • DOI: 10.1063/1.107365

Density functional study on the hole doping of single-layer SnS 2 with metal element X (X = Li, Mg, and Al)
journal, January 2016

  • Yu, Dandan; Liu, Yanyu; Sun, Lili
  • Phys. Chem. Chem. Phys., Vol. 18, Issue 1
  • DOI: 10.1039/C5CP05069C

Thermoelectric properties of p-type polycrystalline SnSe doped with Ag
journal, January 2014

  • Chen, Cheng-Lung; Wang, Heng; Chen, Yang-Yuan
  • Journal of Materials Chemistry A, Vol. 2, Issue 29, p. 11171-11176
  • DOI: 10.1039/c4ta01643b

Photogating carbon nanotube transistors
journal, October 2006

  • Marcus, Matthew S.; Simmons, J. M.; Castellini, O. M.
  • Journal of Applied Physics, Vol. 100, Issue 8
  • DOI: 10.1063/1.2357413

Photoconductivity of biased graphene
journal, December 2012


Probing excitonic states in suspended two-dimensional semiconductors by photocurrent spectroscopy
journal, October 2014

  • Klots, A. R.; Newaz, A. K. M.; Wang, Bin
  • Scientific Reports, Vol. 4, Issue 1
  • DOI: 10.1038/srep06608

Ultrafast Intrinsic Photoresponse and Direct Evidence of Sub-gap States in Liquid Phase Exfoliated MoS2Thin Films
journal, July 2015

  • Ghosh, Sujoy; Winchester, Andrew; Muchharla, Baleeswaraiah
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep11272

Temporary Traps in Silicon and Germanium
journal, April 1953


Soft Lithography
journal, August 1998


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Projector augmented-wave method
journal, December 1994


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Effect of the damping function in dispersion corrected density functional theory
journal, March 2011

  • Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars
  • Journal of Computational Chemistry, Vol. 32, Issue 7
  • DOI: 10.1002/jcc.21759

VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011


Chemical origin of a graphene moiré overlayer on Ru(0001)
journal, January 2008

  • Wang, B.; Bocquet, M. -L.; Marchini, S.
  • Physical Chemistry Chemical Physics, Vol. 10, Issue 24
  • DOI: 10.1039/b801785a

Interfacial coupling in rotational monolayer and bilayer graphene on Ru(0001) from first principles
journal, January 2012


    Works referencing / citing this record:

    Novel structured transition metal dichalcogenide nanosheets
    journal, January 2018

    • Zhang, Xiao; Lai, Zhuangchai; Ma, Qinglang
    • Chemical Society Reviews, Vol. 47, Issue 9
    • DOI: 10.1039/c8cs00094h

    Simultaneous assembly of van der Waals heterostructures into multiple nanodevices
    journal, January 2018

    • Burzurí, Enrique; Vera-Hidalgo, Mariano; Giovanelli, Emerson
    • Nanoscale, Vol. 10, Issue 17
    • DOI: 10.1039/c8nr01045e

    Mechanical and liquid phase exfoliation of cylindrite: a natural van der Waals superlattice with intrinsic magnetic interactions
    journal, May 2019


    Superlattices based on van der Waals 2D materials
    journal, January 2019

    • Ryu, Yu Kyoung; Frisenda, Riccardo; Castellanos-Gomez, Andres
    • Chemical Communications, Vol. 55, Issue 77
    • DOI: 10.1039/c9cc04919c