Anticorrelation between the evolution of molecular dipole moments and induced work function modifications

Journal of Physical Chemistry Letters

Volumn 4, Issue 20, 2013, Pages 3521-3526

  Egger, David A ^a   Zojer, Egbert ^a  

^a GRAZ UNIVERSITY OF TECHNOLOGY   (Austria)

Author keywords

band structure; density functional theory; metal organic interaction; self assembled monolayer; work function modification; zwitterionic molecule

Indexed keywords

ATOMISTIC SIMULATIONS; DONOR-ACCEPTOR MOLECULES; ELECTRONIC LOCALIZATION; METAL-ORGANIC; MOLECULAR DIPOLE; MOLECULAR DIPOLE MOMENT; WORK FUNCTION MODIFICATION; ZWITTER IONIC MOLECULE;

BAND STRUCTURE; DENSITY FUNCTIONAL THEORY; DIPOLE MOMENT; MOLECULES; ORGANIC POLYMERS; SELF ASSEMBLED MONOLAYERS;

WORK FUNCTION;

EID: 84886029327     PISSN: None     EISSN: 19487185     Source Type: Journal    
DOI: 10.1021/jz401721r     Document Type: Article

References (47)

1. Ishii, H.; Sugiyama, K.; Ito, E.; Seki, K. Energy Level Alignment and Interfacial Electronic Structures at Organic/Metal and Organic/Organic Interfaces Adv. Mater. 1999, 11, 605-625
2. Cahen, D.; Kahn, A. Electron Energetics at Surfaces and Interfaces: Concepts and Experiments Adv. Mater. 2003, 15, 271-277
3. Campbell, I.; Rubin, S.; Zawodzinski, T.; Kress, J.; Martin, R.; Smith, D.; Barashkov, N.; Ferraris, J. Controlling Schottky Energy Barriers in Organic Electronic Devices Using Self-Assembled Monolayers Phys. Rev. B 1996, 54, R14321-R14324
4. Boer, B.; de Hadipour, A.; Mandoc, M. M.; Woudenbergh, T.; van Blom, P. W. M. Tuning of Metal Work Functions with Self-Assembled Monolayers Adv. Mater. 2005, 17, 621-625
5. Zhou, Y.; Fuentes-Hernandez, C.; Shim, J.; Meyer, J.; Giordano, A. J.; Li, H.; Winget, P.; Papadopoulos, T.; Cheun, H.; Kim, J. A Universal Method to Produce Low-Work Function Electrodes for Organic Electronics Science 2012, 336, 327-332
6. 3 Tunneling Junctions Comprising Self-Assembled Monolayers J. Phys. Chem. C 2013, 117, 11367-11376
7. Alloway, D. M.; Hofmann, M.; Smith, D. L.; Gruhn, N. E.; Graham, A. L.; Colorado, R.; Wysocki, V. H.; Lee, T. R.; Lee, P. A.; Armstrong, N. R. Interface Dipoles Arising from Self-Assembled Monolayers on Gold: UV-Photoemission Studies of Alkanethiols and Partially Fluorinated Alkanethiols J. Phys. Chem. B 2003, 107, 11690-11699
8. Malicki, M.; Guan, Z.; Ha, S. D.; Heimel, G.; Barlow, S.; Rumi, M.; Kahn, A.; Marder, S. R. Preparation and Characterization of 4′-Donor Substituted Stilbene-4-thiolate Monolayers and Their Influence on the Work Function of Gold Langmuir 2009, 25, 7967-7975
9. Cahen, D.; Naaman, R.; Vager, Z. The Cooperative Molecular Field Effect Adv. Funct. Mater. 2005, 15, 1571-1578
10. Heimel, G.; Romaner, L.; Brédas, J.-L.; Zojer, E. Interface Energetics and Level Alignment at Covalent Metal-Molecule Junctions: π-Conjugated Thiols on Gold Phys. Rev. Lett. 2006, 96, 196806/1-196806/4
11. Heimel, G.; Romaner, L.; Zojer, E.; Brédas, J.-L. Toward Control of the Metal-Organic Interfacial Electronic Structure in Molecular Electronics: A First-Principles Study on Self-Assembled Monolayers of π-Conjugated Molecules on Noble Metals Nano Lett. 2007, 7, 932-940
12. Zangmeister, C. D.; Beebe, J. M.; Naciri, J.; Kushmerick, J. G.; van Zee, R. D. Controlling Charge-Carrier Type in Nanoscale Junctions with Linker Chemistry Small 2008, 4, 1143-1147
13. Schreiber, F. Structure and Growth of Self-Assembling Monolayers Prog. Surf. Sci. 2000, 65, 151-257
14. L'vov, V. S.; Naaman, R.; Tiberkevich, V.; Vager, Z. Cooperative Effect in Electron Transfer Between Metal Substrate and Organized Organic Layers Chem. Phys. Lett. 2003, 381, 650-653
15. Natan, A.; Zidon, Y.; Shapira, Y.; Kronik, L. Cooperative Effects and Dipole Formation at Semiconductor and Self-Assembled-Monolayer Interfaces Phys. Rev. B 2006, 73, 193310
16. Natan, A.; Kronik, L.; Haick, H.; Tung, R. T. Electrostatic Properties of Ideal and Non-ideal Polar Organic Monolayers: Implications for Electronic Devices Adv. Mater. 2007, 19, 4103-4117
17. Cornil, D.; Olivier, Y.; Geskin, V.; Cornil, J. Depolarization Effects in Self-Assembled Monolayers: A Quantum-Chemical Insight Adv. Funct. Mater. 2007, 17, 1143
18. Romaner, L.; Heimel, G.; Ambrosch-Draxl, C.; Zojer, E. The Dielectric Constant of Self-Assembled Monolayers Adv. Funct. Mater. 2008, 18, 3999
19. Monti, O. L. A. Understanding Interfacial Electronic Structure and Charge Transfer: An Electrostatic Perspective J. Phys. Chem. Lett. 2012, 3, 2342-2351
20. Regemorter, T.; Van Guillaume, M.; Fuchs, A.; Lennartz, C.; Geskin, V.; Beljonne, D.; Cornil, J. Methodological Aspects of the Quantum-Chemical Description of Interface Dipoles at Tetrathiafulvalene/tetracyanoquinodimethane Interfaces J. Chem. Phys. 2012, 137, 174708
21. Vager, Z.; Naaman, R. Surprising Electronic-Magnetic Properties of Close-Packed Organized Organic Layers Chem. Phys. 2002, 281, 305-309
22. Kokalj, A. XCrySDen-a New Program for Displaying Crystalline Structures and Electron Densities J. Mol. Graphics Modell. 2000, 17, 176-179
23. Albert, I. D. L.; Marks, T. J.; Ratner, M. A. Conformationally-Induced Geometric Electron Localization. Interrupted Conjugation, Very Large Hyperpolarizabilities, and Sizable Infrared Absorption in Simple Twisted Molecular Chromophores J. Am. Chem. Soc. 1997, 119, 3155-3156
24. Marder, S. R.; Kippelen, B.; Jen, A. K.-Y.; Peyghambarian, N. Design and Synthesis of Chromophores and Polymers for Electro-optic and Photorefractive Applications Nature 1997, 388, 845-851
25. Keinan, S.; Zojer, E.; Brédas, J.-L.; Ratner, M. A.; Marks, T. J. Twisted Π-System Electro-optic Chromophores. A CIS Vs. MRD-CI Theoretical Investigation J. Mol. Struct.: THEOCHEM 2003, 633, 227-235
26. Kang, H.; Facchetti, A.; Zhu, P.; Jiang, H.; Yang, Y.; Cariati, E.; Righetto, S.; Ugo, R.; Zuccaccia, C.; Macchioni, A. Exceptional Molecular Hyperpolarizabilities in Twisted π-Electron System Chromophores Angew. Chem., Int. Ed. 2005, 44, 7922-7925
27. Isborn, C. M.; Davidson, E. R.; Robinson, B. H. Ab Initio Diradical/Zwitterionic Polarizabilities and Hyperpolarizabilities in Twisted Double Bonds J. Phys. Chem. A 2006, 110, 7189-7196
28. Makoudi, Y.; Arab, M.; Palmino, F.; Duverger, E.; Ramseyer, C.; Picaud, F.; Chérioux, F. A Stable Room-Temperature Molecular Assembly of Zwitterionic Organic Dipoles Guided by a Si(111)-7 × 7 Template Effect Angew. Chem., Int. Ed. 2007, 46, 9287-9290
29. Routaboul, L.; Braunstein, P.; Xiao, J.; Zhang, Z.; Dowben, P. A.; Dalmas, G.; Costa, V.; Da Félix, O.; Decher, G.; Rosa, L. G. Altering the Static Dipole on Surfaces through Chemistry: Molecular Films of Zwitterionic Quinonoids J. Am. Chem. Soc. 2012, 134, 8494-8506
30. Che, H.-J.; Chia, P.-J.; Chua, L.-L.; Sivaramakrishnan, S.; Tang, J.-C.; Wee, A. T. S.; Chan, H. S. O.; Ho, P. K. H. Robust Reproducible Large-Area Molecular Rectifier Junctions Appl. Phys. Lett. 2008, 92, 253503
31. Kresse, G.; Furthmüller, J. Efficient Iterative Schemes for Ab Initio Total-Energy Calculations Using a Plane-Wave Basis Set Phys. Rev. B 1996, 54, 11169-11186
32. Bučko, T.; Hafner, J.; ángyán, J. G. Geometry Optimization of Periodic Systems Using Internal Coordinates J. Chem. Phys. 2005, 122, 124508
33. Heyd, J.; Scuseria, G. E.; Ernzerhof, M. Erratum: "Hybrid Functionals Based on a Screened Coulomb Potential" J. Chem. Phys. 2003, 118, 8207
34. J. Chem. Phys. 2006, 124, 219906.
35. Biller, A.; Tamblyn, I.; Neaton, J. B.; Kronik, L. Electronic Level Alignment at a Metal-Molecule Interface from a Short-Range Hybrid Functional J. Chem. Phys. 2011, 135, 164706
36. Rissner, F.; Egger, D. A.; Natan, A.; Körzdörfer, T.; Kümmel, S.; Kronik, L.; Zojer, E. Collectively Induced Quantum-Confined Stark Effect in Monolayers of Molecules Consisting of Polar Repeating Units J. Am. Chem. Soc. 2011, 133, 18634-18645
37. Michaelides, A.; Hu, P.; Lee, M.-H.; Alavi, A.; King, D. Resolution of an Ancient Surface Science Anomaly: Work Function Change Induced by N Adsorption on W{100} Phys. Rev. Lett. 2003, 90, 246103/1-246103/4
38. Bagus, P.; Käfer, D.; Witte, G.; Wöll, C. Work Function Changes Induced by Charged Adsorbates: Origin of the Polarity Asymmetry Phys. Rev. Lett. 2008, 100, 126101
39. Egger, D. A.; Rissner, F.; Rangger, G. M.; Hofmann, O. T.; Wittwer, L.; Heimel, G.; Zojer, E. Self-Assembled Monolayers of Polar Molecules on Au(111) Surfaces: Distributing the Dipoles Phys. Chem. Chem. Phys. 2010, 12, 4291
40. Fukagawa, H.; Kera, S.; Kataoka, T.; Hosoumi, S.; Watanabe, Y.; Kudo, K.; Ueno, N. The Role of the Ionization Potential in Vacuum-Level Alignment at Organic Semiconductor Interfaces Adv. Mater. 2007, 19, 665-668
41. Braun, S.; Salaneck, W. R.; Fahlman, M. Energy-Level Alignment at Organic/Metal and Organic/Organic Interfaces Adv. Mater. 2009, 21, 1450
42. Hauschild, A.; Karki, K.; Cowie, B.; Rohlfing, M.; Tautz, F.; Sokolowski, M. Molecular Distortions and Chemical Bonding of a Large π-Conjugated Molecule on a Metal Surface Phys. Rev. Lett. 2005, 94, 036106
43. Rohlfing, M.; Temirov, R.; Tautz, F. Adsorption Structure and Scanning Tunneling Data of a Prototype Organic-Inorganic Interface: PTCDA on Ag(111) Phys. Rev. B 2007, 76, 115421
44. Greiner, M. T.; Helander, M. G.; Tang, W.-M.; Wang, Z.-B.; Qiu, J.; Lu, Z.-H. Universal Energy-Level Alignment of Molecules on Metal Oxides Nat. Mater. 2011, 11, 76-81
45. Heimel, G.; Duhm, S.; Salzmann, I.; Gerlach, A.; Strozecka, A.; Niederhausen, J.; Bürker, C.; Hosokai, T.; Fernandez-Torrente, I.; Schulze, G. Charged and Metallic Molecular Monolayers through Surface-Induced Aromatic Stabilization Nat. Chem. 2013, 5, 187-194
46. Hofmann, O. T.; Egger, D. A.; Zojer, E. Work-Function Modification Beyond Pinning: When Do Molecular Dipoles Count? Nano Lett. 2010, 10, 4369-4374
47. Miller, D.; Chemla, D.; Damen, T.; Gossard, A.; Wiegmann, W.; Wood, T.; Burrus, C. Band-Edge Electroabsorption in Quantum Well Structures: The Quantum-Confined Stark Effect Phys. Rev. Lett. 1984, 53, 2173-2176