Interfacial charge transfer enhancement via formation of binary molecular assemblies on electronically corrugated boron nitride
Abstract
Using scanning tunneling microscopy/spectroscopy (STM/STS) in conjunction with finite element simulation, we investigate the interfacial behaviors in single-component zinc phthalocyanine (ZnPc) and hexadecafluorinated zinc phthalocyanine (F16ZnPc) molecular overlayers as well as their 1 : 1 mixedphase superstructures on h-BN/Cu(111). We show herein that the formation of the binary molecular superstructure drastically increases the charge transfer between F16ZnPc molecules and the substrate, which is attributed to the greater electrostatic stability of the binary assembly compared to that of the pure phase. This study highlights the significant complication in the design of donor–acceptor molecular thin films as the presence of the substrate, even a weakly interacting one, such as h-BN/metal, can still perturb the intermolecular charge transfer and thereby the physical behaviors of the hybrid system via interfacial processes.
- Publication Date:
- Research Org.:
- Michigan State Univ., East Lansing, MI (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
- OSTI Identifier:
- 1602044
- Alternate Identifier(s):
- OSTI ID: 1575098
- Grant/Contract Number:
- SC0019120
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Chemistry Chemical Physics. PCCP
- Additional Journal Information:
- Journal Volume: 21; Journal Issue: 47; Journal ID: ISSN 1463-9076
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Tan, A., and Zhang, P. P. Interfacial charge transfer enhancement via formation of binary molecular assemblies on electronically corrugated boron nitride. United States: N. p., 2019.
Web. doi:10.1039/c9cp04853g.
Tan, A., & Zhang, P. P. Interfacial charge transfer enhancement via formation of binary molecular assemblies on electronically corrugated boron nitride. United States. https://doi.org/10.1039/c9cp04853g
Tan, A., and Zhang, P. P. Fri .
"Interfacial charge transfer enhancement via formation of binary molecular assemblies on electronically corrugated boron nitride". United States. https://doi.org/10.1039/c9cp04853g. https://www.osti.gov/servlets/purl/1602044.
@article{osti_1602044,
title = {Interfacial charge transfer enhancement via formation of binary molecular assemblies on electronically corrugated boron nitride},
author = {Tan, A. and Zhang, P. P.},
abstractNote = {Using scanning tunneling microscopy/spectroscopy (STM/STS) in conjunction with finite element simulation, we investigate the interfacial behaviors in single-component zinc phthalocyanine (ZnPc) and hexadecafluorinated zinc phthalocyanine (F16ZnPc) molecular overlayers as well as their 1 : 1 mixedphase superstructures on h-BN/Cu(111). We show herein that the formation of the binary molecular superstructure drastically increases the charge transfer between F16ZnPc molecules and the substrate, which is attributed to the greater electrostatic stability of the binary assembly compared to that of the pure phase. This study highlights the significant complication in the design of donor–acceptor molecular thin films as the presence of the substrate, even a weakly interacting one, such as h-BN/metal, can still perturb the intermolecular charge transfer and thereby the physical behaviors of the hybrid system via interfacial processes.},
doi = {10.1039/c9cp04853g},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 47,
volume = 21,
place = {United States},
year = {Fri Nov 15 00:00:00 EST 2019},
month = {Fri Nov 15 00:00:00 EST 2019}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 4 works
Citation information provided by
Web of Science
Web of Science
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:
Tuning Intermolecular Charge Transfer in Donor–Acceptor Two-Dimensional Crystals on Metal Surfaces
journal, October 2017
- Rodríguez-Fernández, Jonathan; Robledo, Maitreyi; Lauwaet, Koen
- The Journal of Physical Chemistry C, Vol. 121, Issue 42
Control of Molecular Organization and Energy Level Alignment by an Electronically Nanopatterned Boron Nitride Template
journal, December 2013
- Joshi, Sushobhan; Bischoff, Felix; Koitz, Ralph
- ACS Nano, Vol. 8, Issue 1
Band-Bending in Organic Semiconductors: the Role of Alkali-Halide Interlayers
journal, December 2013
- Wang, Haibo; Amsalem, Patrick; Heimel, Georg
- Advanced Materials, Vol. 26, Issue 6
Understanding Energy-Level Alignment in Donor–Acceptor/Metal Interfaces from Core-Level Shifts
journal, July 2013
- El-Sayed, Afaf; Borghetti, Patrizia; Goiri, Elizabeth
- ACS Nano, Vol. 7, Issue 8
One-pot growth of two-dimensional lateral heterostructures via sequential edge-epitaxy
journal, January 2018
- Sahoo, Prasana K.; Memaran, Shahriar; Xin, Yan
- Nature, Vol. 553, Issue 7686
Hydrogen-Bonding Fingerprints in Electronic States of Two-Dimensional Supramolecular Assemblies
journal, December 2009
- Gonzalez-Lakunza, Nora; Cañas-Ventura, Marta E.; Ruffieux, Pascal
- ChemPhysChem, Vol. 10, Issue 17
Band alignment of two-dimensional semiconductors for designing heterostructures with momentum space matching
journal, July 2016
- Özçelik, V. Ongun; Azadani, Javad G.; Yang, Ce
- Physical Review B, Vol. 94, Issue 3
Electronic Energy Levels of Weakly Coupled Nanostructures: -Metal Interfaces
journal, July 2008
- Sau, Jay D.; Neaton, J. B.; Choi, Hyoung Joon
- Physical Review Letters, Vol. 101, Issue 2
Quasiparticle and optical spectroscopy of the organic semiconductors pentacene and PTCDA from first principles
journal, March 2012
- Sharifzadeh, Sahar; Biller, Ariel; Kronik, Leeor
- Physical Review B, Vol. 85, Issue 12
Solid-State Energetics and Electrostatics: Madelung Constants and Madelung Energies
journal, January 2012
- Glasser, Leslie
- Inorganic Chemistry, Vol. 51, Issue 4
Electronic structure and current injection in zinc phthalocyanine doped with tetrafluorotetracyanoquinodimethane: Interface versus bulk effects
journal, June 2002
- Gao, Weiying; Kahn, Antoine
- Organic Electronics, Vol. 3, Issue 2
In Situ Observations during Chemical Vapor Deposition of Hexagonal Boron Nitride on Polycrystalline Copper
journal, November 2014
- Kidambi, Piran R.; Blume, Raoul; Kling, Jens
- Chemistry of Materials, Vol. 26, Issue 22
Unexpected interplay of bonding height and energy level alignment at heteromolecular hybrid interfaces
journal, April 2014
- Stadtmüller, Benjamin; Lüftner, Daniel; Willenbockel, Martin
- Nature Communications, Vol. 5, Issue 1
Electronic Structure and Geminate Pair Energetics at Organic–Organic Interfaces: The Case of Pentacene/C 60 Heterojunctions
journal, December 2009
- Verlaak, Stijn; Beljonne, David; Cheyns, David
- Advanced Functional Materials, Vol. 19, Issue 23
Electronic and magnetic properties of molecule-metal interfaces: Transition-metal phthalocyanines adsorbed on Ag(100)
journal, April 2012
- Mugarza, A.; Robles, R.; Krull, C.
- Physical Review B, Vol. 85, Issue 15
Framework for Classifying and Interpreting the Physical Properties of Charge-Transfer Salts of Tcnq: the Unifying Feature of Organic Metals
journal, September 1978
- Torrance, J. B.
- Annals of the New York Academy of Sciences, Vol. 313, Issue 1 Synthesis and
Heterointerface Screening Effects between Organic Monolayers and Monolayer Transition Metal Dichalcogenides
journal, January 2016
- Zheng, Yu Jie; Huang, Yu Li; Chen, Yifeng
- ACS Nano, Vol. 10, Issue 2
Grain Boundary Structures and Electronic Properties of Hexagonal Boron Nitride on Cu(111)
journal, August 2015
- Li, Qiucheng; Zou, Xiaolong; Liu, Mengxi
- Nano Letters, Vol. 15, Issue 9
Organic semiconductor density of states controls the energy level alignment at electrode interfaces
journal, June 2014
- Oehzelt, Martin; Koch, Norbert; Heimel, Georg
- Nature Communications, Vol. 5, Issue 1
Molecularly Resolved Electronic Landscapes of Differing Acceptor–Donor Interface Geometries
journal, March 2018
- Cochrane, Katherine A.; Roussy, Tanya S.; Yuan, Bingkai
- The Journal of Physical Chemistry C, Vol. 122, Issue 15
Boron Nitride on Cu(111): An Electronically Corrugated Monolayer
journal, October 2012
- Joshi, Sushobhan; Ecija, David; Koitz, Ralph
- Nano Letters, Vol. 12, Issue 11
On the Interface Dipole at the Pentacene−Fullerene Heterojunction: A Theoretical Study
journal, February 2010
- Linares, Mathieu; Beljonne, David; Cornil, Jérôme
- The Journal of Physical Chemistry C, Vol. 114, Issue 7
Electrostatic screening mediated by interfacial charge transfer in molecular assemblies on semiconductor substrates
journal, July 2017
- Tan, A.; Wagner, S. R.; Zhang, P. P.
- Physical Review B, Vol. 96, Issue 3
Understanding Charge Transfer in Donor–Acceptor/Metal Systems: A Combined Theoretical and Experimental Study
journal, August 2012
- Cabellos, J. L.; Mowbray, D. J.; Goiri, E.
- The Journal of Physical Chemistry C, Vol. 116, Issue 34
Pronounced polarization-induced energy level shifts at boundaries of organic semiconductor nanostructures
journal, October 2015
- Cochrane, K. A.; Schiffrin, A.; Roussy, T. S.
- Nature Communications, Vol. 6, Issue 1
Image Plane for Surface Potential
journal, June 1986
- Ossicini, S.; Bertoni, C. M.; Gies, P.
- Europhysics Letters (EPL), Vol. 1, Issue 12
Dynamic Jahn-Teller effect in electronic transport through single molecules
journal, December 2008
- Frederiksen, Thomas; Franke, Katharina J.; Arnau, Andrés
- Physical Review B, Vol. 78, Issue 23
Investigating Molecular Charge Transfer Complexes with a Low Temperature Scanning Tunneling Microscope
journal, March 2008
- Jäckel, F.; Perera, U. G. E.; Iancu, V.
- Physical Review Letters, Vol. 100, Issue 12
Probing the energy levels in hole-doped molecular semiconductors
journal, January 2015
- Winkler, Stefanie; Amsalem, Patrick; Frisch, Johannes
- Materials Horizons, Vol. 2, Issue 4
Energetics of metal–organic interfaces: New experiments and assessment of the field
journal, March 2009
- Hwang, Jaehyung; Wan, Alan; Kahn, Antoine
- Materials Science and Engineering: R: Reports, Vol. 64, Issue 1-2
Scanning Tunneling Microscopy and Spectroscopy of Phthalocyanine Molecules on Metal Surfaces
journal, July 2005
- Takada, Masaki; Tada, Hirokazu
- Japanese Journal of Applied Physics, Vol. 44, Issue 7B
Charge-transfer complexes: new perspectives on an old class of compounds
journal, January 2014
- Goetz, Katelyn P.; Vermeulen, Derek; Payne, Margaret E.
- J. Mater. Chem. C, Vol. 2, Issue 17
Interplay between Energy-Level Position and Charging Effect of Manganese Phthalocyanines on an Atomically Thin Insulator
journal, September 2015
- Liu, Liwei; Dienel, Thomas; Widmer, Roland
- ACS Nano, Vol. 9, Issue 10
Integer versus Fractional Charge Transfer at Metal(/Insulator)/Organic Interfaces: Cu(/NaCl)/TCNE
journal, April 2015
- Hofmann, Oliver T.; Rinke, Patrick; Scheffler, Matthias
- ACS Nano, Vol. 9, Issue 5
Reducing the Molecule-Substrate Coupling in -Based Nanostructures by Molecular Interactions
journal, January 2008
- Franke, K. J.; Schulze, G.; Henningsen, N.
- Physical Review Letters, Vol. 100, Issue 3
Charge-separation energy in films of π-conjugated organic molecules
journal, September 2000
- Hill, I. G.; Kahn, A.; Soos, Z. G.
- Chemical Physics Letters, Vol. 327, Issue 3-4
Dielectric properties of hexagonal boron nitride and transition metal dichalcogenides: from monolayer to bulk
journal, March 2018
- Laturia, Akash; Van de Put, Maarten L.; Vandenberghe, William G.
- npj 2D Materials and Applications, Vol. 2, Issue 1
Long Vertical Distance Bonding of the Hexagonal Boron Nitride Monolayer on the Cu(111) Surface
journal, October 2017
- Brülke, Christine; Heepenstrick, Timo; Humberg, Niklas
- The Journal of Physical Chemistry C, Vol. 121, Issue 43
Role of charge transfer, dipole-dipole interactions, and electrostatics in Fermi-level pinning at a molecular heterojunction on a metal surface
journal, January 2013
- Amsalem, P.; Niederhausen, J.; Wilke, A.
- Physical Review B, Vol. 87, Issue 3
Energy Level Realignment in Weakly Interacting Donor–Acceptor Binary Molecular Networks
journal, January 2014
- Zhong, Jian-Qiang; Qin, Xinming; Zhang, Jia-Lin
- ACS Nano, Vol. 8, Issue 2
Renormalization of Molecular Electronic Levels at Metal-Molecule Interfaces
journal, November 2006
- Neaton, J. B.; Hybertsen, Mark S.; Louie, Steven G.
- Physical Review Letters, Vol. 97, Issue 21
Charge transfer and screening in individual molecules on metal substrates: A scanning tunneling spectroscopy and theoretical study
journal, September 2004
- Lu, Xinghua; Grobis, M.; Khoo, K. H.
- Physical Review B, Vol. 70, Issue 11
Properties of copper (fluoro-)phthalocyanine layers deposited on epitaxial graphene
journal, May 2011
- Ren, Jun; Meng, Sheng; Wang, Yi-Lin
- The Journal of Chemical Physics, Vol. 134, Issue 19
Universal energy-level alignment of molecules on metal oxides
journal, November 2011
- Greiner, Mark T.; Helander, Michael G.; Tang, Wing-Man
- Nature Materials, Vol. 11, Issue 1
Donor–anion interactions in quarter-filled low-dimensional organic conductors
journal, January 2018
- Pouget, Jean-Paul; Alemany, Pere; Canadell, Enric
- Materials Horizons, Vol. 5, Issue 4
Band renormalization of a polymer physisorbed on graphene investigated by many-body perturbation theory
journal, August 2012
- Puschnig, Peter; Amiri, Peiman; Draxl, Claudia
- Physical Review B, Vol. 86, Issue 8
Exploring the F 16 CoPc/Ag(110) Interface Using Scanning Tunneling Microscopy and Spectroscopy. 2. Adsorption-Induced Charge Transfer Effect
journal, November 2010
- Toader, Marius; Gopakumar, Thiruvancheril G.; Shukrynau, Pavel
- The Journal of Physical Chemistry C, Vol. 114, Issue 49
Self-assembly of organic molecules at metal surfaces
journal, April 2009
- Kühnle, Angelika
- Current Opinion in Colloid & Interface Science, Vol. 14, Issue 2
Hexagonal boron nitride on transition metal surfaces
journal, February 2013
- Gómez Díaz, Jaime; Ding, Yun; Koitz, Ralph
- Theoretical Chemistry Accounts, Vol. 132, Issue 4
Formation of Dispersive Hybrid Bands at an Organic-Metal Interface
journal, April 2008
- Gonzalez-Lakunza, N.; Fernández-Torrente, I.; Franke, K. J.
- Physical Review Letters, Vol. 100, Issue 15
Quantum-Chemical Characterization of the Origin of Dipole Formation at Molecular Organic/Organic Interfaces
journal, February 2009
- Avilov, Igor; Geskin, Victor; Cornil, Jérôme
- Advanced Functional Materials, Vol. 19, Issue 4
Energy-Level Alignment at Organic/Metal and Organic/Organic Interfaces
journal, April 2009
- Braun, Slawomir; Salaneck, William R.; Fahlman, Mats
- Advanced Materials, Vol. 21, Issue 14-15, p. 1450-1472
Modeling charge transfer at organic donor-acceptor semiconductor interfaces
journal, May 2012
- Çakir, Deniz; Bokdam, Menno; de Jong, Michel P.
- Applied Physics Letters, Vol. 100, Issue 20
Visualizing coherent intermolecular dipole–dipole coupling in real space
journal, March 2016
- Zhang, Yang; Luo, Yang; Zhang, Yao
- Nature, Vol. 531, Issue 7596
Design of Organic Semiconductors from Molecular Electrostatics †
journal, February 2011
- Heimel, Georg; Salzmann, Ingo; Duhm, Steffen
- Chemistry of Materials, Vol. 23, Issue 3
Strain distributions and their influence on electronic structures of WSe2–MoS2 laterally strained heterojunctions
journal, January 2018
- Zhang, Chendong; Li, Ming-Yang; Tersoff, Jerry
- Nature Nanotechnology, Vol. 13, Issue 2
Orientation-controlled charge transfer at CuPc/F16CuPc interfaces
journal, September 2009
- Chen, Wei; Chen, Shuang; Chen, Shi
- Journal of Applied Physics, Vol. 106, Issue 6
Energetics of molecular interfaces
journal, July 2005
- Cahen, David; Kahn, Antoine; Umbach, Eberhard
- Materials Today, Vol. 8, Issue 7
Multi-Component Organic Layers on Metal Substrates
journal, December 2015
- Goiri, Elizabeth; Borghetti, Patrizia; El-Sayed, Afaf
- Advanced Materials, Vol. 28, Issue 7
Analyze chemisorbed organic/metal interface by combining the two sub-interfaces model and the integer charge transfer model
journal, April 2019
- Du, Ying-Ying; Li, Wen-Jie; Chen, Guang-Hua
- AIP Advances, Vol. 9, Issue 4
Structural and electronic properties of a large-scale Moiré pattern of hexagonal boron nitride on Cu(111) studied with density functional theory
journal, January 2013
- Koitz, Ralph; Seitsonen, Ari P.; Iannuzzi, Marcella
- Nanoscale, Vol. 5, Issue 12
Corrugation in the Weakly Interacting Hexagonal-BN/Cu(111) System: Structure Determination by Combining Noncontact Atomic Force Microscopy and X-ray Standing Waves
journal, September 2017
- Schwarz, Martin; Riss, Alexander; Garnica, Manuela
- ACS Nano, Vol. 11, Issue 9
Anomalous Coarsening Driven by Reversible Charge Transfer at Metal–Organic Interfaces
journal, November 2014
- Della Pia, Ada; Riello, Massimo; Floris, Andrea
- ACS Nano, Vol. 8, Issue 12
Fingerprint of Fractional Charge Transfer at the Metal/Organic Interface
journal, May 2015
- Savu, Sabine-A.; Biddau, Giulio; Pardini, Lorenzo
- The Journal of Physical Chemistry C, Vol. 119, Issue 22
Energy level alignment regimes at hybrid organic–organic and inorganic–organic interfaces
journal, February 2007
- Braun, Slawomir; Osikowicz, Wojciech; Wang, Ying
- Organic Electronics, Vol. 8, Issue 1
Vibronic Spectroscopy of Single C 60 Molecules and Monolayers with the STM †
journal, May 2005
- Pradhan, Nilay A.; Liu, Ning; Ho, Wilson
- The Journal of Physical Chemistry B, Vol. 109, Issue 17
Bonding and Charge Transfer in Metal–Organic Coordination Networks on Au(111) with Strong Acceptor Molecules
journal, November 2012
- Faraggi, Marisa N.; Jiang, Nan; Gonzalez-Lakunza, Nora
- The Journal of Physical Chemistry C, Vol. 116, Issue 46
Energy Level Bending in Ultrathin Polymer Layers Obtained through Langmuir-Shäfer Deposition
journal, December 2015
- Bao, Qinye; Fabiano, Simone; Andersson, Mattias
- Advanced Functional Materials, Vol. 26, Issue 7
Band structure engineering in organic semiconductors
journal, June 2016
- Schwarze, M.; Tress, W.; Beyer, B.
- Science, Vol. 352, Issue 6292
Fermi-level pinning appears upon weak electrode-organic contact without gap states: A universal phenomenon
journal, September 2017
- Yang, Jin-Peng; Shang, Lin-Tai; Bussolotti, Fabio
- Organic Electronics, Vol. 48
The Madelung Constant of Organic Salts
journal, November 2009
- Izgorodina, Ekaterina I.; Bernard, Uditha L.; Dean, Pamela M.
- Crystal Growth & Design, Vol. 9, Issue 11
Calculating the Universal Energy-Level Alignment of Organic Molecules on Metal Oxides
journal, October 2012
- Ley, Lothar; Smets, Yaou; Pakes, Christopher I.
- Advanced Functional Materials, Vol. 23, Issue 7
Selective adsorption and electronic interaction of on epitaxial graphene
journal, December 2010
- Wang, Yi-Lin; Ren, Jun; Song, Can-Li
- Physical Review B, Vol. 82, Issue 24
The Effect of Fluorination on Pentacene/Gold Interface Energetics and Charge Reorganization Energy
journal, January 2007
- Koch, N.; Vollmer, A.; Duhm, S.
- Advanced Materials, Vol. 19, Issue 1
Controlling Coordination Reactions and Assembly on a Cu(111) Supported Boron Nitride Monolayer
journal, February 2015
- Urgel, José I.; Schwarz, Martin; Garnica, Manuela
- Journal of the American Chemical Society, Vol. 137, Issue 7
Molecular Insight Into the Energy Levels at the Organic Donor/Acceptor Interface: A Quantum Mechanics/Molecular Mechanics Study
journal, July 2011
- Yost, Shane R.; Wang, Lee-Ping; Van Voorhis, Troy
- The Journal of Physical Chemistry C, Vol. 115, Issue 29
Structural and Electronic Properties of (TMTTF)2X Salts with Tetrahedral Anions
journal, March 2018
- Rösslhuber, Roland; Rose, Eva; Ivek, Tomislav
- Crystals, Vol. 8, Issue 3
Strong electron-phonon coupling at a metal/organic interface: PTCDA/Ag(111)
journal, February 2002
- Tautz, F. S.; Eremtchenko, M.; Schaefer, J. A.
- Physical Review B, Vol. 65, Issue 12
Dielectric response and electric properties of organic semiconducting phthalocyanine thin films
journal, August 2012
- Saleh, A. M.; Hraibat, S. M.; Kitaneh, R. M-L.
- Journal of Semiconductors, Vol. 33, Issue 8
Energy Level Alignment and Interfacial Electronic Structures at Organic/Metal and Organic/Organic Interfaces
journal, June 1999
- Ishii, Hisao; Sugiyama, Kiyoshi; Ito, Eisuke
- Advanced Materials, Vol. 11, Issue 8, p. 605-625
Boron nitride on Cu(111): an electronically corrugated monolayer
text, January 2012
- Joshi, Sushobhan; Ecija, David; Koitz, Ralph
- American Chemical Society
Structural and electronic properties of a large-scale Moiré pattern of hexagonal boron nitride on Cu(111) studied with density functional theory
text, January 2013
- Koitz, Ralph; Seitsonen, Ari P.; Iannuzzi, Marcella
- RSC Publishing
Control of molecular organization and energy level alignment by an electronically nanopatterned boron nitride template
text, January 2014
- Sushobhan, Joshi,; Felix, Bischoff,; Ralph, Koitz,
- American Chemical Society (ACS)
Hexagonal boron nitride on transition metal surfaces
text, January 2013
- Gomez Diaz, Jaime; Ding, Yun; Koitz, Ralph
- Springer
Probing the energy levels in hole-doped molecular semiconductors
text, January 2015
- Winkler, Stefanie; Amsalem, Patrick; Frisch, Johannes
- Humboldt-Universität zu Berlin
Band renormalization of a polymer physisorbed on graphene investigated by many-body perturbation theory
text, January 2012
- Puschnig, Peter; Amiri, Peiman; Draxl, Claudia
- arXiv