Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Metallic behavior in the graphene analogue Ni3(HITP)2 and a strategy to render the material a semiconductor.

Abstract

The metal organic framework material Ni3(2,3,6,7,10,11 - hexaiminotriphenylene)2, (Ni3(HITP)2) is composed of layers of extended conjugated planes analogous to graphene. We carried out Density functional theory (DFT) calculations to model the electronic structure of bulk and monolayer Ni3(HITP)2. The layered 3D material is metallic, similar to graphene. Our calculations predict that there is appreciable band dispersion not only in-plane, but perpendicular to the stacking planes as well, suggesting that, unlike graphene, the conductivity may be nearly isotropic. In contrast, a 2D monolayer of the material exhibits a band gap, consistent with previously published results. Insight obtained from studies of the evolution of the material from semiconducting to metallic as the material is transitioned from 2D to 3D suggests the possibility of modifying the material to render it semiconducting by changing the metal center and inserting spacer moieties between the layers. Furthermore, the DFT calculations predict that the modified material will be structurally stable and exhibit a band gap.

Authors:
 [1];  [2];  [1];  [1]
+ Show Author Affiliations
  1. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  2. Drexel Univ., Philadelphia, PA (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Renewable Power Office. Solar Energy Technologies Office
OSTI Identifier:
1252693
Report Number(s):
SAND-2016-1018J
Journal ID: ISSN 1932-7447; 619121
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 120; Journal Issue: 27; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Foster, Michael E., Sohlberg, Karl, Spataru, Dan Catalin, and Allendorf, Mark D. Metallic behavior in the graphene analogue Ni3(HITP)2 and a strategy to render the material a semiconductor.. United States: N. p., 2016. Web. doi:10.1021/acs.jpcc.6b05746.
Copy to clipboard
Foster, Michael E., Sohlberg, Karl, Spataru, Dan Catalin, & Allendorf, Mark D. Metallic behavior in the graphene analogue Ni3(HITP)2 and a strategy to render the material a semiconductor.. United States. https://doi.org/10.1021/acs.jpcc.6b05746
Copy to clipboard
Foster, Michael E., Sohlberg, Karl, Spataru, Dan Catalin, and Allendorf, Mark D. Sun . "Metallic behavior in the graphene analogue Ni3(HITP)2 and a strategy to render the material a semiconductor.". United States. https://doi.org/10.1021/acs.jpcc.6b05746. https://www.osti.gov/servlets/purl/1252693.
Copy to clipboard
@article{osti_1252693,
title = {Metallic behavior in the graphene analogue Ni3(HITP)2 and a strategy to render the material a semiconductor.},
author = {Foster, Michael E. and Sohlberg, Karl and Spataru, Dan Catalin and Allendorf, Mark D.},
abstractNote = {The metal organic framework material Ni3(2,3,6,7,10,11 - hexaiminotriphenylene)2, (Ni3(HITP)2) is composed of layers of extended conjugated planes analogous to graphene. We carried out Density functional theory (DFT) calculations to model the electronic structure of bulk and monolayer Ni3(HITP)2. The layered 3D material is metallic, similar to graphene. Our calculations predict that there is appreciable band dispersion not only in-plane, but perpendicular to the stacking planes as well, suggesting that, unlike graphene, the conductivity may be nearly isotropic. In contrast, a 2D monolayer of the material exhibits a band gap, consistent with previously published results. Insight obtained from studies of the evolution of the material from semiconducting to metallic as the material is transitioned from 2D to 3D suggests the possibility of modifying the material to render it semiconducting by changing the metal center and inserting spacer moieties between the layers. Furthermore, the DFT calculations predict that the modified material will be structurally stable and exhibit a band gap.},
doi = {10.1021/acs.jpcc.6b05746},
journal = {Journal of Physical Chemistry. C},
number = 27,
volume = 120,
place = {United States},
year = {Sun Jun 19 00:00:00 EDT 2016},
month = {Sun Jun 19 00:00:00 EDT 2016}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpcc.6b05746
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 56 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Nobel Lecture: Graphene: Materials in the Flatland
journal, August 2011

Graphene synthesis by ion implantation
journal, November 2010

  • Garaj, Slaven; Hubbard, William; Golovchenko, J. A.
  • Applied Physics Letters, Vol. 97, Issue 18
  • DOI: 10.1063/1.3507287

Near room-temperature synthesis of transfer-free graphene films
journal, January 2012

  • Kwak, Jinsung; Chu, Jae Hwan; Choi, Jae-Kyung
  • Nature Communications, Vol. 3, Issue 1
  • DOI: 10.1038/ncomms1650

Solid-source growth and atomic-scale characterization of graphene on Ag(111)
journal, November 2013

  • Kiraly, Brian; Iski, Erin V.; Mannix, Andrew J.
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3804

Graphene-Like Two-Dimensional Materials
journal, January 2013

  • Xu, Mingsheng; Liang, Tao; Shi, Minmin
  • Chemical Reviews, Vol. 113, Issue 5, p. 3766-3798
  • DOI: 10.1021/cr300263a

Electronics based on two-dimensional materials
journal, October 2014

  • Fiori, Gianluca; Bonaccorso, Francesco; Iannaccone, Giuseppe
  • Nature Nanotechnology, Vol. 9, Issue 10
  • DOI: 10.1038/nnano.2014.207

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

Molecular Semiconductors in Organic Photovoltaic Cells
journal, November 2010

  • Hains, Alexander W.; Liang, Ziqi; Woodhouse, Michael A.
  • Chemical Reviews, Vol. 110, Issue 11
  • DOI: 10.1021/cr9002984

Hybrid porous solids past, present, future
journal, January 2008

  • Férey, Gérard
  • Chem. Soc. Rev., Vol. 37, Issue 1, p. 191-214
  • DOI: 10.1039/B618320B

Soft porous crystal meets TCNQ: charge transfer-type porous coordination polymers
journal, January 2011

  • Shimomura, Satoru; Kitagawa, Susumu
  • Journal of Materials Chemistry, Vol. 21, Issue 15
  • DOI: 10.1039/c1jm10208g

Reticular synthesis and the design of new materials
journal, June 2003

  • Yaghi, Omar M.; O'Keeffe, Michael; Ockwig, Nathan W.
  • Nature, Vol. 423, Issue 6941, p. 705-714
  • DOI: 10.1038/nature01650

Metal–Organic Framework Thin Films: From Fundamentals to Applications.
journal, September 2011

  • Bétard, Angélique; Fischer, Roland A.
  • Chemical Reviews, Vol. 112, Issue 2, p. 1055-1083
  • DOI: 10.1021/cr200167v

Cation-Dependent Intrinsic Electrical Conductivity in Isostructural Tetrathiafulvalene-Based Microporous Metal–Organic Frameworks
journal, January 2015

  • Park, Sarah S.; Hontz, Eric R.; Sun, Lei
  • Journal of the American Chemical Society, Vol. 137, Issue 5
  • DOI: 10.1021/ja512437u

Million-Fold Electrical Conductivity Enhancement in Fe 2 (DEBDC) versus Mn 2 (DEBDC) (E = S, O)
journal, May 2015

  • Sun, Lei; Hendon, Christopher H.; Minier, Mikael A.
  • Journal of the American Chemical Society, Vol. 137, Issue 19
  • DOI: 10.1021/jacs.5b02897

Porous, Conductive Metal-Triazolates and Their Structural Elucidation by the Charge-Flipping Method
journal, June 2012

  • Gándara, Felipe; Uribe-Romo, Fernando J.; Britt, David K.
  • Chemistry - A European Journal, Vol. 18, Issue 34, p. 10595-10601
  • DOI: 10.1002/chem.201103433

Conductivity, Doping, and Redox Chemistry of a Microporous Dithiolene-Based Metal−Organic Framework
journal, July 2010

  • Kobayashi, Yoji; Jacobs, Benjamin; Allendorf, Mark D.
  • Chemistry of Materials, Vol. 22, Issue 14
  • DOI: 10.1021/cm101238m

Tunable Electrical Conductivity in Metal-Organic Framework Thin-Film Devices
journal, December 2013

  • Talin, A. Alec; Centrone, Andrea; Ford, Alexandra C.
  • Science, Vol. 343, Issue 6166, p. 66-69
  • DOI: 10.1126/science.1246738

Cu 3 (hexaiminotriphenylene) 2 : An Electrically Conductive 2D Metal-Organic Framework for Chemiresistive Sensing
journal, February 2015

  • Campbell, Michael G.; Sheberla, Dennis; Liu, Sophie F.
  • Angewandte Chemie International Edition, Vol. 54, Issue 14
  • DOI: 10.1002/anie.201411854

High Electrical Conductivity in Ni 3 (2,3,6,7,10,11-hexaiminotriphenylene) 2 , a Semiconducting Metal–Organic Graphene Analogue
journal, April 2014

  • Sheberla, Dennis; Sun, Lei; Blood-Forsythe, Martin A.
  • Journal of the American Chemical Society, Vol. 136, Issue 25
  • DOI: 10.1021/ja502765n

Quantum spin Hall and Z 2 metallic states in an organic material
journal, November 2014

Metal–organic Kagome lattices M 3 (2,3,6,7,10,11-hexaiminotriphenylene) 2 (M = Ni and Cu): from semiconducting to metallic by metal substitution
journal, January 2015

  • Chen, Shuang; Dai, Jun; Zeng, Xiao Cheng
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 8
  • DOI: 10.1039/C4CP05328A

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994

  • Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.
  • The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627
  • DOI: 10.1021/j100096a001

Consistent Gaussian basis sets of triple-zeta valence with polarization quality for solid-state calculations
journal, October 2012

  • Peintinger, Michael F.; Oliveira, Daniel Vilela; Bredow, Thomas
  • Journal of Computational Chemistry, Vol. 34, Issue 6
  • DOI: 10.1002/jcc.23153

Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

C RYSTAL14 : A program for the ab initio investigation of crystalline solids
journal, March 2014

  • Dovesi, Roberto; Orlando, Roberto; Erba, Alessandro
  • International Journal of Quantum Chemistry, Vol. 114, Issue 19
  • DOI: 10.1002/qua.24658

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

Corrections to density-functional theory band gaps
journal, December 1998

Definitive Band Gaps for Single-Wall Carbon Nanotubes
journal, September 2010

  • Matsuda, Yuki; Tahir-Kheli, Jamil; Goddard, William A.
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 19
  • DOI: 10.1021/jz100889u

Influence of the exchange screening parameter on the performance of screened hybrid functionals
journal, December 2006

  • Krukau, Aliaksandr V.; Vydrov, Oleg A.; Izmaylov, Artur F.
  • The Journal of Chemical Physics, Vol. 125, Issue 22
  • DOI: 10.1063/1.2404663

Electronic band structure of zirconia and hafnia polymorphs from the G W perspective
journal, February 2010

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

Solvent-Assisted Linker Exchange: An Alternative to the De Novo Synthesis of Unattainable Metal-Organic Frameworks
journal, March 2014

  • Karagiaridi, Olga; Bury, Wojciech; Mondloch, Joseph E.
  • Angewandte Chemie International Edition, Vol. 53, Issue 18
  • DOI: 10.1002/anie.201306923

MOFs, MILs and more: concepts, properties and applications for porous coordination networks (PCNs)
journal, January 2010

  • Janiak, Christoph; Vieth, Jana K.
  • New Journal of Chemistry, Vol. 34, Issue 11
  • DOI: 10.1039/c0nj00275e

Stepwise Synthesis of Metal–Organic Frameworks Replacement of Structural Organic Linkers
journal, July 2011

  • Burnett, Brandon J.; Barron, Paul M.; Hu, Chunhua
  • Journal of the American Chemical Society, Vol. 133, Issue 26, p. 9984-9987
  • DOI: 10.1021/ja201911v

Intrinsic concentration, effective densities of states, and effective mass in silicon
journal, March 1990

  • Green, Martin A.
  • Journal of Applied Physics, Vol. 67, Issue 6
  • DOI: 10.1063/1.345414

Highest-Occupied-Molecular-Orbital Band Dispersion of Rubrene Single Crystals as Observed by Angle-Resolved Ultraviolet Photoelectron Spectroscopy
journal, April 2010

Photoinduced Charge-Carrier Generation in Epitaxial MOF Thin Films: High Efficiency as a Result of an Indirect Electronic Band Gap?
journal, May 2015

  • Liu, Jinxuan; Zhou, Wencai; Liu, Jianxi
  • Angewandte Chemie International Edition, Vol. 54, Issue 25
  • DOI: 10.1002/anie.201501862

Conductive metal–organic frameworks and networks: fact or fantasy?
journal, January 2012

  • Hendon, Christopher H.; Tiana, Davide; Walsh, Aron
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 38, p. 13120-13132
  • DOI: 10.1039/c2cp41099k
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Origin of the Chemiresistive Response of Ultrathin Films of Conductive Metal–Organic Frameworks
    journal, November 2018

    • Rubio‐Giménez, Víctor; Almora‐Barrios, Neyvis; Escorcia‐Ariza, Garin
    • Angewandte Chemie International Edition, Vol. 57, Issue 46
    • DOI: 10.1002/anie.201808242

    Origin of metallicity in 2D multilayer nickel bis(dithiolene) sheets
    journal, June 2018

    Pressure-induced metallicity and piezoreductive transition of metal-centres in conductive 2-dimensional metal–organic frameworks
    journal, January 2019

    • Le, Khoa N.; Hendon, Christopher H.
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 46
    • DOI: 10.1039/c9cp04797b

    Origin of the Chemiresistive Response of Ultrathin Films of Conductive Metal–Organic Frameworks
    journal, October 2018

    • Rubio‐Giménez, Víctor; Almora‐Barrios, Neyvis; Escorcia‐Ariza, Garin
    • Angewandte Chemie, Vol. 130, Issue 46
    • DOI: 10.1002/ange.201808242

    Electrically Conducting Nanocomposites of Carbon Nanotubes and Metal‐Organic Frameworks with Strong Interactions between the two Components
    journal, July 2019

    • Schulze, Hendrik A.; Hoppe, Bastian; Schäfer, Malte
    • ChemNanoMat, Vol. 5, Issue 9
    • DOI: 10.1002/cnma.201900110

    Graphene-like metal-organic frameworks: Morphology control, optimization of thin film electrical conductivity and fast sensing applications
    other, January 2018

    • Hoppe, Bastian; Hindricks, Karen D. J.; Warwas, Dawid P.
    • Cambridge : Royal Society of Chemistry
    • DOI: 10.15488/4168
      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: