Publisher’s Note: Self-Assembly of Bicomponent Molecular Monolayers: Adsorption Height Changes and Their Consequences [Phys. Rev. Lett. 112, 117602 (2014)]

Goiri, E.; Matena, Manfred; El-Sayed, Afaf; Lobo-Checa, Jorge; Borghetti, Patrizia; Rogero, Celia; Detlefs, Blanka; Duvernay, J.; Ortega, J. E.; Oteyza, Dimas G. de

doi:10.1103/physrevlett.112.149901

Cited by 9 publications

(11 citation statements)

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“…donor and acceptor molecules) form mixed monolayers on the metal substrate, this canonical relationship is broken, as has been discussed in detail elsewhere 22,[93][94][95] . With hindsight, it is not surprising that these quantities are closely related, because all of them are connected to the molecular π-electron system.…”

Section: Resultsmentioning

confidence: 97%

The interplay between interface structure, energy level alignment and chemical bonding strength at organic–metal interfaces

Willenbockel

Lüftner

Stadtmüller

et al. 2015

Phys. Chem. Chem. Phys.

101

144

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What do energy level alignments at metal-organic interfaces reveal about the metal-molecule bonding strength? Is it permissible to take vertical adsorption heights as indicators of bonding strengths? In this paper we analyse 3,4,9,10-perylene-tetracarboxylic acid dianhydride (PTCDA) on the three canonical low index Ag surfaces to provide exemplary answers to these questions. Specifically, we employ angular resolved photoemission spectroscopy for a systematic study of the energy level alignments of the two uppermost frontier states in ordered monolayer phases of PTCDA. Data are analysed using the orbital tomography approach. This allows the unambiguous identification of the orbital character of these states, and also the discrimination between inequivalent species. Combining this experimental information with DFT calculations and the generic Newns-Anderson chemisorption model, we analyse the alignments of highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO) with respect to the vacuum levels of bare and molecule-covered surfaces. This reveals clear differences between the two frontier states. In particular, on all surfaces the LUMO is subject to considerable bond stabilization through the interaction between the molecular π-electron system and the metal, as a consequence of which it also becomes occupied. Moreover, we observe a larger bond stabilization for the more open surfaces. Most importantly, our analysis shows that both the orbital binding energies of the LUMO and the overall adsorption heights of the molecule are linked to the strength of the chemical interaction between the molecular π-electron system and the metal, in the sense that stronger bonding leads to shorter adsorption heights and larger orbital binding energies.

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Section: Resultsmentioning

confidence: 97%

The interplay between interface structure, energy level alignment and chemical bonding strength at organic–metal interfaces

Willenbockel

Lüftner

Stadtmüller

et al. 2015

Phys. Chem. Chem. Phys.

101

144

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“…One approach for increasing the intermolecular interactions is based on the decoration of the organic molecules with complementary functional groups, e.g., hydrogen‐bond donating and accepting groups . In the last few years, the use of fluorinated molecules in mixed molecular layers leading to hydrogen‐fluorine bonds was studied intensely . Besides the increased intermolecular interaction of fluorinated molecules with hydrogen‐bond donating molecules, the fluorination induces electron accepting character and based on their hydrogen‐fluorine bonds, strong intermolecular interaction can be achieved .…”

Section: Introductionmentioning

confidence: 99%

Triphenylene‐Derived Electron Acceptors and Donors on Ag(111): Formation of Intermolecular Charge‐Transfer Complexes with Common Unoccupied Molecular States

Müller

Schmidt

Link

et al. 2019

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Over the past years, ultrathin films consisting of electron donating and accepting molecules have attracted increasing attention due to their potential usage in optoelectronic devices. Key parameters for understanding and tuning their performance are intermolecular and molecule–substrate interactions. Here, the formation of a monolayer thick blend of triphenylene‐based organic donor and acceptor molecules from 2,3,6,7,10,11‐hexamethoxytriphenylene (HAT) and 1,4,5,8,9,12‐hexaazatriphenylenehexacarbonitrile (HATCN), respectively, on a silver (111) surface is reported. Scanning tunneling microscopy and spectroscopy, valence and core level photoelectron spectroscopy, as well as low‐energy electron diffraction measurements are used, complemented by density functional theory calculations, to investigate both the electronic and structural properties of the homomolecular as well as the intermixed layers. The donor molecules are weakly interacting with the Ag(111) surface, while the acceptor molecules show a strong interaction with the substrate leading to charge transfer and substantial buckling of the top silver layer and of the adsorbates. Upon mixing acceptor and donor molecules, strong hybridization occurs between the two different molecules leading to the emergence of a common unoccupied molecular orbital located at both the donor and acceptor molecules. The donor acceptor blend studied here is, therefore, a compelling candidate for organic electronics based on self‐assembled charge‐transfer complexes.

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“…CuPc on coinage metal surfaces has been characterized with several experimental techniques, such as as scanning tunneling microscopy (STM), x-ray standing wave (XSW), and ultraviolet photoemission spectroscopy (UPS) [39,47]. Recently, this molecule has been utilized in a multicomponent blend with perfluoropentacene (PFP) in order to study the modification of the interfacial properties with respect to the single-component system [30]. Nevertheless, these systems are particularly challenging for standard DFT functionals.…”

Section: Complex Charge Rearrangement: Copper Phthalocyanine On Smentioning

confidence: 99%

“…In this regard, much progress has been made using a variety of different techniques, from doping methods [25,26] to charge carrier injector/acceptor layers [27][28][29] and stacking layers [20,30]. In general, a chemisorbed monolayer with a pronounced polar orientation is usually associated with a large , on the order of 2-3 eV [31].…”

Section: Motivation and Previous Workmentioning

confidence: 99%

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Electronic charge rearrangement at metal/organic interfaces induced by weak van der Waals interactions

Ferri

Ambrosetti

Tkatchenko

2017

Phys. Rev. Materials

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Electronic charge rearrangements at interfaces between organic molecules and solid surfaces play a key role in a wide range of applications in catalysis, light-emitting diodes, single-molecule junctions, molecular sensors and switches, and photovoltaics. It is common to utilize electrostatics and Pauli pushback to control the interface electronic properties, while the ubiquitous van der Waals (vdW) interactions are often considered to have a negligible direct contribution (beyond the obvious structural relaxation). Here, we apply a fully self-consistent Tkatchenko-Scheffler vdW density functional to demonstrate that the weak vdW interactions can induce sizable charge rearrangements at hybrid metal/organic systems (HMOS). The complex vdW correlation potential smears out the interfacial electronic density, thereby reducing the charge transfer in HMOS, changes the interface work functions by up to 0.2 eV, and increases the interface dipole moment by up to 0.3 Debye. Our results suggest that vdW interactions should be considered as an additional control parameter in the design of hybrid interfaces with the desired electronic properties.

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Publisher’s Note: Self-Assembly of Bicomponent Molecular Monolayers: Adsorption Height Changes and Their Consequences [Phys. Rev. Lett. 112, 117602 (2014)]

Cited by 9 publications

References 0 publications

The interplay between interface structure, energy level alignment and chemical bonding strength at organic–metal interfaces

The interplay between interface structure, energy level alignment and chemical bonding strength at organic–metal interfaces

Triphenylene‐Derived Electron Acceptors and Donors on Ag(111): Formation of Intermolecular Charge‐Transfer Complexes with Common Unoccupied Molecular States

Electronic charge rearrangement at metal/organic interfaces induced by weak van der Waals interactions

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