Formation of Occupied and Unoccupied Hybrid Bands at Interfaces between Metals and Organic Donors/Acceptors

Gerbert, David; Hofmann, Oliver; Tegeder, Petra

doi:10.1021/acs.jpcc.8b09606

Cited by 12 publications

(23 citation statements)

References 59 publications

(100 reference statements)

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“…To study the role of adatoms, we chose F4TCNQ on Au(111), since multiple independent studies have found that it readily and reproducibly forms well-ordered structures containing adatoms as part of the adlayer. 35 , 44 , 46 , 47 The surface structure consists of only one F4TCNQ molecule and one adatom per unit cell, which reduces the computational effort and facilitates the analysis of this system (compared to larger unit cells). The strong interactions between the adsorbate and substrate lifts the herringbone reconstruction of Au(111), and the F4TCNQ molecule-Au-adatom network is arranged in a Au(111) surface supercell, as shown in Figure 1 .…”

Section: Resultsmentioning

confidence: 99%

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Role of Adatoms for the Adsorption of F4TCNQ on Au(111)

et al. 2022

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Organic adlayers on inorganic substrates often contain adatoms, which can be incorporated within the adsorbed molecular species, forming two-dimensional metal–organic frameworks at the substrate surface. The interplay between native adatoms and adsorbed molecules significantly changes various adlayer properties such as the adsorption geometry, the bond strength between the substrate and the adsorbed species, or the work function at the interface. Here, we use dispersion-corrected density functional theory to gain insight into the energetics that drive the incorporation of native adatoms within molecular adlayers based on the prototypical, experimentally well-characterized system of F4TCNQ on Au(111). We explain the adatom-induced modifications in the adsorption geometry and the adsorption energy based on the electronic structure and charge transfer at the interface.

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Section: Resultsmentioning

confidence: 99%

“…In this work, we used the “tight” defaults, which were shown to yield converged results in a previous work. 44 Going beyond these settings, we furthermore increased the onset of the basis set cutoff potential from the default of 4 to 6 Å in order to obtain adsorption energies converged within 1 meV (see Supporting Information ).…”

Section: Methodsmentioning

confidence: 99%

Role of Adatoms for the Adsorption of F4TCNQ on Au(111)

et al. 2022

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“…P4O exhibits a similar chemisorptive behavior on Cu(111), but physisorbs on Au(111) 73,78 . In contrast, F 4 TCNQ chemisorbs on virtually all clean metal surfaces 58,66,329, [439][440][441][442][443][444][445] showing a qualitatively similar behavior. These systems shall hence be discussed as model systems for strongly coupled organic-metal interfaces.…”

Section: Strongly Interacting Systemsmentioning

confidence: 95%

Binding and Electronic Level Alignment of $\boldsymbolπ$-Conjugated Systems on Metals

Franco-Cañellas,

Duhm,

Gerlach

et al. 2020

Preprint

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We review the binding and energy level alignment of π-conjugated systems on metals, a field which during the last two decades has seen tremendous progress both in terms of experimental characterization as well as in the depth of theoretical understanding. Precise measurements of vertical adsorption distances and the electronic structure together with ab-initio calculations have shown that most of the molecular systems have to be considered as intermediate cases between weak physisorption and strong chemisorption. In this regime, the subtle interplay of different effects such as covalent bonding, charge transfer, electrostatic and van der Waals interactions yields a complex situation with different adsorption mechanisms. In order to establish a better understanding of the binding and the electronic level alignment of π-conjugated molecules on metals, we provide an up-to-date overview of the literature, explain the fundamental concepts as well as the experimental techniques and discuss typical case studies. Thereby, we relate the geometric with the electronic structure in a consistent picture and cover the entire range from weak to strong coupling.

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“…Hybridization is a necessary prerequisite for interfacial band formation which can be identified via dispersing states in angle-resolved photoemission experiments. Interfacial band formation has been shown in the case of strong electron acceptors (tetrafluoro-tetracyanoquinodimethane (F 4 TCNQ)/Au(111), 39,40 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA)/ Ag(110) 41 and 1,4,5,8-naphthalenetetracarboxylicdi-anhydride (NTCDA)/Ag(111) 41,42 ) and a donor (tetrathiafulvalene (TTF)/Au(111) 40 ) adsorbed on noble metal surfaces. Recently, we demonstrated interfacial band formation for a N-heteropolycyclic molecule, a 1,3,8,10tetraazaperopyrene derivative (TAPP-CF 3 , see Fig.…”

Section: Introductionmentioning

confidence: 99%

“…This state has an effective mass of m * = -0.86 ± 0.24 m e .While hybridization between molecular and metal states occurs in many organic/metal systems, experimental evidence for interfacial band formation via dispersing electronic states is rarely observed. Only for strong electron acceptors (F4TCNQ/Au(111),39,40 PTCDA/ Ag(110),41 NTCDA/Ag(110)42 ) or a donor (TTF/Au(111)40 ), dispersing interface bands have been proposed. In all cases a charge transfer between molecular states and the surface state of the metallic substrate appears (Fermi-level pinning).…”

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confidence: 99%