ACS Publications. Most Trusted. Most Cited. Most Read

OR SEARCH CITATIONS

My Activity
Publications
CONTENT TYPES

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Phys. Chem. C 2016, 120, 18, 9904-9913
RETURN TO ISSUEPREVArticleNEXT

Structural and Vibrational Properties of CuPc/Ag(111) Ultrathin Films

View Author Information
Fachbereich Physik und Wissenschaftliches Zentrum für Materialwissenschaften der Philipps - Universität Marburg, Renthof 5, D-35032 Marburg, Germany
*Tel +49-6421-2824328; Fax +49-6421-2824218; e-mail [email protected] (P.J.).
Cite this: J. Phys. Chem. C 2016, 120, 18, 9904–9913
Publication Date (Web):April 18, 2016
https://doi.org/10.1021/acs.jpcc.6b02837
Copyright © 2016 American Chemical Society
RIGHTS & PERMISSIONS

Article Views

1122

Altmetric

-

Citations

24
LEARN ABOUT THESE METRICS
Read OnlinePDF (2 MB)
Get e-Alerts
Supporting Info (1)»
SUBJECTS:

Abstract

Abstract Image

The initial stages of copper(II)–phthalocyanine (CuPc) thin film growth on Ag(111) have been investigated using Fourier transform infrared absorption spectroscopy (FT-IRAS), spot profile analysis low-energy electron diffraction (SPA-LEED), and thermal desorption spectroscopy (TDS). Starting at (sub)monolayer coverages up to 5 monolayers (ML), a number of ordered overlayers are found. Vibrational spectroscopy shows characteristic spectroscopic signatures for the individual submonolayer phases as well as for the bilayer, trilayer, and multilayers. Highly asymmetric line shapes of the in-plane vibrational modes of submonolayer CuPc provide unequivocal evidence for interfacial dynamical charge transfer between the metal electronic states and CuPc molecular orbitals, indicative for a partially filled LUMO at the Fermi energy as well as the prevalence of severe nonadiabaticity in the electron–vibron coupling. Growth of the second and third CuPc layers proceeds in a layer-by-layer fashion (Frank van der Merwe growth). Higher layers deposited at 300 K, on the other hand, transform into 3D crystallites on top of the CuPc trilayer upon annealing. For CuPc/Ag(111) monolayers thermal desorption spectra reveal intact CuPc desorption for coverages above 0.9 ML. At lower coverages an alternative reaction path involving partial dissociation of the CuPc molecules is found, with 1/4 Pc as the desorbing stable product species. In this study IR absorption spectra have been obtained at an exceptionally high spectral resolution of 0.5 cm–1, which allows a spectral discrimination of molecular species with unprecedented detail. Specifically, CuPc mono-, bi-, and trilayers as well as the bulk-like crystalline phase of CuPc have been discriminated based on clearly resolved, closely spaced vibrational bands.

Supporting Information

ARTICLE SECTIONS
Jump To

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.6b02837.

  • Long-range order of CuPc molecular layers (coverage regime 0.9–10 ML) from SPALEED images (PDF)

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Cited By

This article is cited by 24 publications.

  1. Laura Fernández, Sebastian Thussing, Anton X. Brión-Ríos, Daniel Sánchez-Portal, Peter Jakob. Lateral Interactions and Order–Disorder Phase Transitions of Metal Phthalocyanines on Ag(111). The Journal of Physical Chemistry C 2021, 125 (28) , 15623-15635. https://doi.org/10.1021/acs.jpcc.1c03948
  2. Alfred John Weymouth, Elisabeth Riegel, Bianca Simmet, Oliver Gretz, Franz J. Giessibl. Lateral Force Microscopy Reveals the Energy Barrier of a Molecular Switch. ACS Nano 2021, 15 (2) , 3264-3271. https://doi.org/10.1021/acsnano.0c09965
  3. Roberto Costantini, Cesare Grazioli, Albano Cossaro, Luca Floreano, Alberto Morgante, Martina Dell’Angela. Pump–Probe X-ray Photoemission Reveals Light-Induced Carrier Accumulation in Organic Heterojunctions. The Journal of Physical Chemistry C 2020, 124 (49) , 26603-26612. https://doi.org/10.1021/acs.jpcc.0c07530
  4. Sebastian Thussing, Sebastian Flade, Kristjan Eimre, Carlo A. Pignedoli, Roman Fasel, Peter Jakob. Reaction Pathway toward Seven-Atom-Wide Armchair Graphene Nanoribbon Formation and Identification of Intermediate Species on Au(111). The Journal of Physical Chemistry C 2020, 124 (29) , 16009-16018. https://doi.org/10.1021/acs.jpcc.0c04596
  5. F. Widdascheck, M. Kothe, S. Thussing, P. Jakob, G. Witte. Evolution of TiOPc Films on Au(111): From Seed Layer to Crystalline Multilayers. The Journal of Physical Chemistry C 2020, 124 (27) , 14664-14671. https://doi.org/10.1021/acs.jpcc.0c03244
  6. Michael Kothe, Gregor Witte. Orientational and Crystalline Order of Copper–Phthalocyanine Films on Gold: the Role of Substrate Roughness and Cleanliness. Langmuir 2019, 35 (42) , 13570-13577. https://doi.org/10.1021/acs.langmuir.9b02658
  7. Jens Niederhausen, Yuan Zhang, Fairoja Cheenicode Kabeer, Yves Garmshausen, Bernd M. Schmidt, Yang Li, Kai-Felix Braun, Stefan Hecht, Alexandre Tkatchenko, Norbert Koch, Saw-Wai Hla. Subtle Fluorination of Conjugated Molecules Enables Stable Nanoscale Assemblies on Metal Surfaces. The Journal of Physical Chemistry C 2018, 122 (33) , 18902-18911. https://doi.org/10.1021/acs.jpcc.8b03398
  8. Qi Wang, Antoni Franco-Cañellas, Penghui Ji, Christoph Bürker, Rong-Bin Wang, Katharina Broch, Pardeep Kumar Thakur, Tien-Lin Lee, Haiming Zhang, Alexander Gerlach, Lifeng Chi, Steffen Duhm, Frank Schreiber. Bilayer Formation vs Molecular Exchange in Organic Heterostructures: Strong Impact of Subtle Changes in Molecular Structure. The Journal of Physical Chemistry C 2018, 122 (17) , 9480-9490. https://doi.org/10.1021/acs.jpcc.8b01529
  9. Alexander Mänz, Alrun Aline Hauke, and Gregor Witte . Copper Phthalocyanine as Contact Layers for Pentacene Films Grown on Coinage Metals. The Journal of Physical Chemistry C 2018, 122 (4) , 2165-2172. https://doi.org/10.1021/acs.jpcc.7b10324
  10. Sebastian Thussing and Peter Jakob . Thermal Stability and Interlayer Exchange Processes in Heterolayers of CuPc and PTCDA on Ag(111). The Journal of Physical Chemistry C 2017, 121 (25) , 13680-13691. https://doi.org/10.1021/acs.jpcc.7b02377
  11. Laura Fernández, Sebastian Thussing, Alexander Mänz, Gregor Witte, Anton X. Brion-Rios, Pepa Cabrera-Sanfelix, Daniel Sanchez-Portal, and Peter Jakob . Structural and Vibrational Properties of the TiOPc Monolayer on Ag(111). The Journal of Physical Chemistry C 2017, 121 (3) , 1608-1617. https://doi.org/10.1021/acs.jpcc.6b09701
  12. Xiaofang Wang, Zhong Long, Ren Bin, Ruilong Yang, Qifa Pan, Fangfang Li, Lizhu Luo, Yin Hu, and Kezhao Liu . Study of the Decomposition and Phase Transition of Uranium Nitride under UHV Conditions via TDS, XRD, SEM, and XPS. Inorganic Chemistry 2016, 55 (21) , 10835-10838. https://doi.org/10.1021/acs.inorgchem.6b01260
  13. Th. Schmidt, T. Wilkens, J. Falta. Ordering of copper phthalocyanine films on functionalized Si(111). Surface Science 2022, 725 , 122127. https://doi.org/10.1016/j.susc.2022.122127
  14. Martin Stöhr, Mainak Sadhukhan, Yasmine S. Al-Hamdani, Jan Hermann, Alexandre Tkatchenko. Coulomb interactions between dipolar quantum fluctuations in van der Waals bound molecules and materials. Nature Communications 2021, 12 (1) https://doi.org/10.1038/s41467-020-20473-w
  15. P. Jakob, S. Thussing. Vibrational Frequency Used as Internal Clock Reference to Access Molecule-Metal Charge-Transfer Times. Physical Review Letters 2021, 126 (11) https://doi.org/10.1103/PhysRevLett.126.116801
  16. Stefan R. Kachel, Pierre-Martin Dombrowski, Tobias Breuer, J. Michael Gottfried, Gregor Witte. Engineering of TMDC–OSC hybrid interfaces: the thermodynamics of unitary and mixed acene monolayers on MoS 2. Chemical Science 2021, 12 (7) , 2575-2585. https://doi.org/10.1039/D0SC05633B
  17. Antoni Franco-Cañellas, Steffen Duhm, Alexander Gerlach, Frank Schreiber. Binding and electronic level alignment of π -conjugated systems on metals. Reports on Progress in Physics 2020, 83 (6) , 066501. https://doi.org/10.1088/1361-6633/ab7a42
  18. Elisabeth Wruss, Georgia Prokopiou, Leeor Kronik, Egbert Zojer, Oliver T. Hofmann, David A. Egger. Magnetic configurations of open-shell molecules on metals: The case of CuPc and CoPc on silver. Physical Review Materials 2019, 3 (8) https://doi.org/10.1103/PhysRevMaterials.3.086002
  19. S Thussing, L Fernández, P Jakob. Thermal stability and interlayer exchange processes in heterolayers of TiOPc and PTCDA on Ag(1 1 1). Journal of Physics: Condensed Matter 2019, 31 (13) , 134002. https://doi.org/10.1088/1361-648X/aafcf8
  20. Felix Widdascheck, Alrun Aline Hauke, Gregor Witte. A Solvent‐Free Solution: Vacuum‐Deposited Organic Monolayers Modify Work Functions of Noble Metal Electrodes. Advanced Functional Materials 2019, 29 (17) , 1808385. https://doi.org/10.1002/adfm.201808385
  21. N L Zaitsev, P Jakob, R Tonner. Structure and vibrational properties of the PTCDA/Ag(1 1 1) interface: bilayer versus monolayer. Journal of Physics: Condensed Matter 2018, 30 (35) , 354001. https://doi.org/10.1088/1361-648X/aad576
  22. Agata Sabik, Franciszek Gołek, Grażyna Antczak. Thermal desorption and stability of cobalt phthalocyanine on Ag(100). Applied Surface Science 2018, 435 , 894-902. https://doi.org/10.1016/j.apsusc.2017.11.149
  23. Mainak Sadhukhan, Alexandre Tkatchenko. Long-Range Repulsion Between Spatially Confined van der Waals Dimers. Physical Review Letters 2017, 118 (21) https://doi.org/10.1103/PhysRevLett.118.210402
  24. Laura Fernandez, Sebastian Thussing, Alexander Mänz, Jörg Sundermeyer, Gregor Witte, Peter Jakob. The discrete nature of inhomogeneity: the initial stages and local configurations of TiOPc during bilayer growth on Ag(111). Physical Chemistry Chemical Physics 2017, 19 (3) , 2495-2502. https://doi.org/10.1039/C6CP07922A

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

You’ve supercharged your research process with ACS and Mendeley!

STEP 1:
Click to create an ACS ID

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

MENDELEY PAIRING EXPIRED
Your Mendeley pairing has expired. Please reconnect