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Title: Tunable two-dimensional interfacial coupling in molecular heterostructures

Abstract

Two-dimensional van der Waals heterostructures are of considerable interest for the next generation nanoelectronics because of their unique interlayer coupling and optoelectronic properties. Here, we report a modified Langmuir–Blodgett method to organize twodimensional molecular charge transfer crystals into arbitrarily and vertically stacked heterostructures, consisting of bis(ethylenedithio)tetrathiafulvalene (BEDT–TTF)/C 60 and poly (3-dodecylthiophene-2,5-diyl) (P3DDT)/C 60 nanosheets. A strong and anisotropic interfacial coupling between the charge transfer pairs is demonstrated. The van der Waals heterostructures exhibit pressure dependent sensitivity with a high piezoresistance coefficient of -4.4 × 10 -6 Pa -1, and conductance and capacitance tunable by external stimuli (ferroelectric field and magnetic field). Density functional theory calculations confirm charge transfer between the n-orbitals of the S atoms in BEDT–TTF of the BEDT–TTF/C 60 layer and the π* orbitals of C atoms in C 60 of the P3DDT/C 60 layer contribute to the inter-complex CT. Thus, the two-dimensional molecular van der Waals heterostructures with tunable optical–electronic–magnetic coupling properties are promising for flexible electronic applications.

Authors:
 [1];  [2];  [3];  [1];  [4];  [1]
  1. Temple Univ., Philadelphia, PA (United States). Dept. of Mechanical Engineering and Temple Materials Inst.
  2. Temple Univ., Philadelphia, PA (United States). Dept. of Chemistry and Inst. for Computational Molecular Science and Center for the Computational Design of Functional Layered Materials
  3. Temple Univ., Philadelphia, PA (United States). Dept. of Chemistry and Inst. for Computational Molecular Science
  4. Temple Univ., Philadelphia, PA (United States). Temple Materials Inst. and Dept. of Chemistry and Inst. for Computational Molecular Science
Publication Date:
Research Org.:
Temple Univ., Philadelphia, PA (United States); Energy Frontier Research Centers (EFRC) (United States). Center for the Computational Design of Functional Layered Materials (CCDM)
Sponsoring Org.:
USDOE Office of Science (SC)Basic Energy Sciences (BES) (SC-22); US Army Research Office (ARO); National Science Foundation (NSF); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
OSTI Identifier:
1425646
Grant/Contract Number:  
SC0012575; OCI-0725070; ACI-1238993; AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Molecular self-assembly; Organic molecules in materials science

Citation Formats

Xu, Beibei, Chakraborty, Himanshu, Yadav, Vivek K., Zhang, Zhuolei, Klein, Michael L., and Ren, Shenqiang. Tunable two-dimensional interfacial coupling in molecular heterostructures. United States: N. p., 2017. Web. doi:10.1038/s41467-017-00390-1.
Xu, Beibei, Chakraborty, Himanshu, Yadav, Vivek K., Zhang, Zhuolei, Klein, Michael L., & Ren, Shenqiang. Tunable two-dimensional interfacial coupling in molecular heterostructures. United States. doi:10.1038/s41467-017-00390-1.
Xu, Beibei, Chakraborty, Himanshu, Yadav, Vivek K., Zhang, Zhuolei, Klein, Michael L., and Ren, Shenqiang. Tue . "Tunable two-dimensional interfacial coupling in molecular heterostructures". United States. doi:10.1038/s41467-017-00390-1. https://www.osti.gov/servlets/purl/1425646.
@article{osti_1425646,
title = {Tunable two-dimensional interfacial coupling in molecular heterostructures},
author = {Xu, Beibei and Chakraborty, Himanshu and Yadav, Vivek K. and Zhang, Zhuolei and Klein, Michael L. and Ren, Shenqiang},
abstractNote = {Two-dimensional van der Waals heterostructures are of considerable interest for the next generation nanoelectronics because of their unique interlayer coupling and optoelectronic properties. Here, we report a modified Langmuir–Blodgett method to organize twodimensional molecular charge transfer crystals into arbitrarily and vertically stacked heterostructures, consisting of bis(ethylenedithio)tetrathiafulvalene (BEDT–TTF)/C60 and poly (3-dodecylthiophene-2,5-diyl) (P3DDT)/C60 nanosheets. A strong and anisotropic interfacial coupling between the charge transfer pairs is demonstrated. The van der Waals heterostructures exhibit pressure dependent sensitivity with a high piezoresistance coefficient of -4.4 × 10-6 Pa-1, and conductance and capacitance tunable by external stimuli (ferroelectric field and magnetic field). Density functional theory calculations confirm charge transfer between the n-orbitals of the S atoms in BEDT–TTF of the BEDT–TTF/C60 layer and the π* orbitals of C atoms in C60 of the P3DDT/C60 layer contribute to the inter-complex CT. Thus, the two-dimensional molecular van der Waals heterostructures with tunable optical–electronic–magnetic coupling properties are promising for flexible electronic applications.},
doi = {10.1038/s41467-017-00390-1},
journal = {Nature Communications},
issn = {2041-1723},
number = 1,
volume = 8,
place = {United States},
year = {2017},
month = {8}
}

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Works referenced in this record:

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

Rational Design of Charge-Transfer Interactions in Halogen-Bonded Co-crystals toward Versatile Solid-State Optoelectronics
journal, August 2015

  • Zhu, Weigang; Zheng, Renhui; Zhen, Yonggang
  • Journal of the American Chemical Society, Vol. 137, Issue 34
  • DOI: 10.1021/jacs.5b05586

Enhanced charge separation in organic photovoltaic films doped with ferroelectric dipoles
journal, January 2012

  • Nalwa, Kanwar S.; Carr, John A.; Mahadevapuram, Rakesh C.
  • Energy & Environmental Science, Vol. 5, Issue 5
  • DOI: 10.1039/c2ee03478f

Bimolecular recombination in polymer/fullerene bulk heterojunction solar cells
journal, January 2006

  • Koster, L. J. A.; Mihailetchi, V. D.; Blom, P. W. M.
  • Applied Physics Letters, Vol. 88, Issue 5
  • DOI: 10.1063/1.2170424

Carbon nanomaterials for electronics, optoelectronics, photovoltaics, and sensing
journal, January 2013

  • Jariwala, Deep; Sangwan, Vinod K.; Lauhon, Lincoln J.
  • Chem. Soc. Rev., Vol. 42, Issue 7
  • DOI: 10.1039/C2CS35335K

Multiferroicity of Carbon-Based Charge-Transfer Magnets
journal, November 2014


Progress in organic single-crystal field-effect transistors
journal, January 2013

  • Lezama, Ignacio Gutiérrez; Morpurgo, Alberto F.
  • MRS Bulletin, Vol. 38, Issue 1
  • DOI: 10.1557/mrs.2012.311

Solution-Processed Molecular Opto-Ferroic Crystals
journal, March 2016


Charge Trapping in Intergrain Regions of Pentacene Thin Film Transistors
journal, December 2008

  • Tello, Marta; Chiesa, Marco; Duffy, Claudia M.
  • Advanced Functional Materials, Vol. 18, Issue 24
  • DOI: 10.1002/adfm.200800009

Giant piezoresistance effect in silicon nanowires
journal, October 2006


Control of spreading and drying of a polymer solution from Marangoni flows
journal, November 2007


A Free-Standing Molecular Spin-Charge Converter for Ubiquitous Magnetic-Energy Harvesting and Sensing
journal, December 2016

  • Xu, Beibei; Chakraborty, Himanshu; Remsing, Richard C.
  • Advanced Materials, Vol. 29, Issue 8
  • DOI: 10.1002/adma.201605150

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

Estimation of interfacial tension between organic liquids and water
journal, November 1993

  • Demond, Avery H.; Lindner, Angela S.
  • Environmental Science & Technology, Vol. 27, Issue 12
  • DOI: 10.1021/es00048a004

Nanowire Ultraviolet Photodetectors and Optical Switches
journal, January 2002


Electrically tunable transverse magnetic focusing in graphene
journal, February 2013

  • Taychatanapat, Thiti; Watanabe, Kenji; Taniguchi, Takashi
  • Nature Physics, Vol. 9, Issue 4
  • DOI: 10.1038/nphys2549

QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009

  • Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
  • Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
  • DOI: 10.1088/0953-8984/21/39/395502

Chemically Driven Interfacial Coupling in Charge-Transfer Mediated Functional Superstructures
journal, March 2016


Molecular crystals on two-dimensional van der Waals substrates
journal, January 2015


Low magnetic field response single-phase multiferroics under high temperature
journal, January 2015

  • Wang, Jianlin; Fu, Zhengping; Peng, Ranran
  • Materials Horizons, Vol. 2, Issue 2
  • DOI: 10.1039/C4MH00202D

Millimeter-Sized Molecular Monolayer Two-Dimensional Crystals
journal, March 2011


Epitaxial Growth of Molecular Crystals on van der Waals Substrates for High-Performance Organic Electronics
journal, January 2014

  • Lee, Chul-Ho; Schiros, Theanne; Santos, Elton J. G.
  • Advanced Materials, Vol. 26, Issue 18
  • DOI: 10.1002/adma.201304973

Advances of flexible pressure sensors toward artificial intelligence and health care applications
journal, January 2015

  • Zang, Yaping; Zhang, Fengjiao; Di, Chong-an
  • Materials Horizons, Vol. 2, Issue 2
  • DOI: 10.1039/C4MH00147H

General observation of n-type field-effect behaviour in organic semiconductors
journal, March 2005

  • Chua, Lay-Lay; Zaumseil, Jana; Chang, Jui-Fen
  • Nature, Vol. 434, Issue 7030
  • DOI: 10.1038/nature03376

Two-dimensional quasi-freestanding molecular crystals for high-performance organic field-effect transistors
journal, October 2014

  • He, Daowei; Zhang, Yuhan; Wu, Qisheng
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms6162

Charge-Transfer Magnetoelectrics of Polymeric Multiferroics
journal, March 2014

  • Qin, Wei; Jasion, Daniel; Chen, Xiaomin
  • ACS Nano, Vol. 8, Issue 4
  • DOI: 10.1021/nn500323j

Multiferroicity in an organic charge-transfer salt that is suggestive of electric-dipole-driven magnetism
journal, August 2012

  • Lunkenheimer, Peter; Müller, Jens; Krohns, Stephan
  • Nature Materials, Vol. 11, Issue 9
  • DOI: 10.1038/nmat3400

High-performance solution-processed polymer ferroelectric field-effect transistors
journal, February 2005

  • Naber, Ronald C. G.; Tanase, Cristina; Blom, Paul W. M.
  • Nature Materials, Vol. 4, Issue 3
  • DOI: 10.1038/nmat1329

Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006

  • Grimme, Stefan
  • Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
  • DOI: 10.1002/jcc.20495

Soft self-consistent pseudopotentials in a generalized eigenvalue formalism
journal, April 1990


Intrinsic Charge Transport on the Surface of Organic Semiconductors
journal, August 2004


Wavelike charge density fluctuations and van der Waals interactions at the nanoscale
journal, March 2016

  • Ambrosetti, Alberto; Ferri, Nicola; DiStasio, Robert A.
  • Science, Vol. 351, Issue 6278
  • DOI: 10.1126/science.aae0509

Enhancement of Transport Characteristics in Poly(3-hexylthiophene) Films Deposited with Floating Film Transfer Method
journal, November 2009

  • Morita, Takeomi; Singh, Vipul; Nagamatsu, Shuichi
  • Applied Physics Express, Vol. 2, Issue 11
  • DOI: 10.1143/APEX.2.111502

Avogadro: an advanced semantic chemical editor, visualization, and analysis platform
journal, August 2012

  • Hanwell, Marcus D.; Curtis, Donald E.; Lonie, David C.
  • Journal of Cheminformatics, Vol. 4, Issue 1
  • DOI: 10.1186/1758-2946-4-17

Intrinsic electrical conductivity of nanostructured metal-organic polymer chains
journal, April 2013

  • Hermosa, Cristina; Vicente Álvarez, Jose; Azani, Mohammad-Reza
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms2696

Space-Charge Limited Photocurrent
journal, April 2005


Perovskite-perovskite tandem photovoltaics with optimized band gaps
journal, October 2016


Magnetic-Field Effects in Organic Semiconducting Materials and Devices
journal, April 2009


Two-dimensional flexible nanoelectronics
journal, December 2014

  • Akinwande, Deji; Petrone, Nicholas; Hone, James
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms6678

Highly conductive self-assembled nanoribbons of coordination polymers
journal, December 2009

  • Welte, Lorena; Calzolari, Arrigo; Di Felice, Rosa
  • Nature Nanotechnology, Vol. 5, Issue 2
  • DOI: 10.1038/nnano.2009.354

Scaling laws for van der Waals interactions in nanostructured materials
journal, August 2013

  • Gobre, Vivekanand V.; Tkatchenko, Alexandre
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3341

Van der Waals epitaxy—a new epitaxial growth method for a highly lattice-mismatched system
journal, August 1992


Atomically thin p–n junctions with van der Waals heterointerfaces
journal, August 2014

  • Lee, Chul-Ho; Lee, Gwan-Hyoung; van der Zande, Arend M.
  • Nature Nanotechnology, Vol. 9, Issue 9
  • DOI: 10.1038/nnano.2014.150

All-polymeric control of nanoferronics
journal, December 2015


Origin of the light intensity dependence of the short-circuit current of polymer/fullerene solar cells
journal, November 2005

  • Koster, L. J. A.; Mihailetchi, V. D.; Xie, H.
  • Applied Physics Letters, Vol. 87, Issue 20
  • DOI: 10.1063/1.2130396

Use of Piezoresistive Materials in the Measurement of Displacement, Force, and Torque
journal, October 1957

  • Mason, W. P.; Thurston, R. N.
  • The Journal of the Acoustical Society of America, Vol. 29, Issue 10
  • DOI: 10.1121/1.1908710

An X-ray crystallographic analysis of a (BEDT-TTF)2C60 charge-transfer complex
journal, January 1992

  • Izuoka, Akira; Tachikawa, Tatsuya; Sugawara, Tadashi
  • Journal of the Chemical Society, Chemical Communications, Issue 19
  • DOI: 10.1039/c39920001472