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:
-
- Sandia National Lab. (SNL-CA), Livermore, CA (United States)
- 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.
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
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.
@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}
}
Web of Science
Works referenced in this record:
Nobel Lecture: Graphene: Materials in the Flatland
journal, August 2011
- Novoselov, K. S.
- Reviews of Modern Physics, Vol. 83, Issue 3
Graphene synthesis by ion implantation
journal, November 2010
- Garaj, Slaven; Hubbard, William; Golovchenko, J. A.
- Applied Physics Letters, Vol. 97, Issue 18
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
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
Graphene-Like Two-Dimensional Materials
journal, January 2013
- Xu, Mingsheng; Liang, Tao; Shi, Minmin
- Chemical Reviews, Vol. 113, Issue 5, p. 3766-3798
Electronics based on two-dimensional materials
journal, October 2014
- Fiori, Gianluca; Bonaccorso, Francesco; Iannaccone, Giuseppe
- Nature Nanotechnology, Vol. 9, Issue 10
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
Molecular Semiconductors in Organic Photovoltaic Cells
journal, November 2010
- Hains, Alexander W.; Liang, Ziqi; Woodhouse, Michael A.
- Chemical Reviews, Vol. 110, Issue 11
Hybrid porous solids past, present, future
journal, January 2008
- Férey, Gérard
- Chem. Soc. Rev., Vol. 37, Issue 1, p. 191-214
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
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
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
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
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
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
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
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
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
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
Quantum spin Hall and metallic states in an organic material
journal, November 2014
- Zhao, Bao; Zhang, Jiayong; Feng, Wanxiang
- Physical Review B, Vol. 90, Issue 20
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
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
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
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
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
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
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
Corrections to density-functional theory band gaps
journal, December 1998
- Johnson, Kurt A.; Ashcroft, N. W.
- Physical Review B, Vol. 58, Issue 23
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
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
Electronic band structure of zirconia and hafnia polymorphs from the perspective
journal, February 2010
- Jiang, Hong; Gomez-Abal, Ricardo I.; Rinke, Patrick
- Physical Review B, Vol. 81, Issue 8
Intrinsic Charge Transport on the Surface of Organic Semiconductors
journal, August 2004
- Podzorov, V.; Menard, E.; Borissov, A.
- Physical Review Letters, Vol. 93, Issue 8, Article No. 086602
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
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
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
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
Highest-Occupied-Molecular-Orbital Band Dispersion of Rubrene Single Crystals as Observed by Angle-Resolved Ultraviolet Photoelectron Spectroscopy
journal, April 2010
- Machida, Shin-ichi; Nakayama, Yasuo; Duhm, Steffen
- Physical Review Letters, Vol. 104, Issue 15
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
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
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
Origin of metallicity in 2D multilayer nickel bis(dithiolene) sheets
journal, June 2018
- Li, Suchun; Lü, Tie-Yu; Zheng, Jin-Cheng
- 2D Materials, Vol. 5, Issue 3
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
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
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
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