Binding groups for highly ordered SAM formation: carboxylic versus thiol

Krzykawska, Anna; Ossowski, Jakub; Żaba, Tomasz; Cyganik, Piotr

doi:10.1039/c7cc01939d

Cited by 26 publications

(37 citation statements)

References 27 publications

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“…[ 10,11b ] For NC‐NapS/Ag and NC‐NapSe/Ag this component is located at a BE of ≈284.7 eV and for NC‐NapCOO/Ag at a lower BE of ≈284.2 eV. Following the established analysis for analogous SAMs based on aromatic thiols and carboxylic acids [ 12a,b,20 ] this shift toward the lower BE by ≈0.5 eV can be attributed to the interfacial charge rearrangement. Such a collective electrostatic effect is most likely associated with the presence of an interfacial dipole layer [ 21 ] oriented toward the substrate as a result of AgO bond formation, which has an ionic character.…”

Section: Resultsmentioning

confidence: 93%

“…The O 1s range for NC‐NapCOO/Ag in Figure 1f can be fitted by a single and symmetric peak at BE ≈530.6 eV, which confirms the formation of well‐defined bidentate carboxylateAg bond mediated by the COO group. [ 12a,b,19 ]…”

Section: Resultsmentioning

confidence: 99%

“…To this end, in the current study we take a step in this direction by dealing with Ag(111) substrate instead of Au(111) and by expanding the types of the anchoring group to carboxylic acid, which became increasingly popular recently in the context of molecular self‐assembly. [ 12 ] Once again, we use intentionally SAMs with the naphthalene backbone and nitrile tail group, as schematically presented in Figure a, as they allow us to compare results of the current and former [ 10,11c,13 ] experiments and calculations, involving complementary techniques such as X‐ray photoelectron spectroscopy (XPS), near‐edge X‐ray absorption fine structure (NEXAFS) spectroscopy, secondary ion mass spectrometry (SIMS), water contact angle (WCA) goniometry, conductivity measurements using‐large area molecular junctions with liquid metal electrode (EGaIn), and calculations by using DFT. As to the selection of silver as the substrate, it is well justified by its highest conductivity among metals, better accessibility compared to gold which is the most commonly used material for electrodes in molecular electronics, [ 2a–c ] and the very limited number of thermal stability studies [ 14 ] of SAMs formed on this substrate, with none of them addressing correlation of this parameter with the conductance.…”

Section: Introductionmentioning

confidence: 99%

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Thermally Stable and Highly Conductive SAMs on Ag Substrate—The Impact of the Anchoring Group

Wróbel

Żaba

Sauter

et al. 2021

Adv Elect Materials

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Self‐assembled monolayers (SAMs) on metal substrates are an important part of modern interfacial chemistry and nanotechnology. The robustness of SAMs strongly depends on their thermal stability, which, together with electric conductivity, crucial for their applications in molecular/organic electronics. In this context, using a multidisciplinary approach, the structure, stability, and conductivity properties of conjugated aromatic SAMs featuring the naphthalene backbone and S, Se, or COO group, mediating bonding to the Ag substrate are addressed. Whereas thermal stability of these SAMs exhibits a strong dependence on anchoring group, their conductivity is similar, which is rationalized by tentative model considering redistribution of charge density along the molecular framework. The thermal stability of model naphthalenethiol SAM, emphasized by desorption energy of ≈1.69 eV, is better than that of typical N‐heterocyclic carbene (NHC) monolayers considered currently as the most stable SAMs on metal substrates. However, in contrast to NHC SAMs, which are highly insulating, the naphtalene‐based SAM, with S, Se or COO anchoring groups, are highly conductive, even in comparison with analogous oligophenyl SAMs (by a factor of 10). A unique combination of the ultimate thermal stability and superior conductivity for the naphthalenethiol SAM on Ag makes it highly attractive for applications.

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Section: Resultsmentioning

confidence: 93%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Thermally Stable and Highly Conductive SAMs on Ag Substrate—The Impact of the Anchoring Group

Wróbel

Żaba

Sauter

et al. 2021

Adv Elect Materials

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“…[62][63][64][65]73 In these studies Au/mica substrates were used onto which a Ag bilayer or a pseudomorphic (√3×√3)R30° Cu layer were electrochemically deposited in the region positive of the Nernst potential (underpotential deposition, UPD) 74 Notably, a very recent STM study demonstrated that also Ag films are suitable substrates for the assembly of ArCA SAMs. 75 H3BTB was chosen since, as seen from Scheme 1, it is closely related to the two other tricarboxylic acid molecules which, in previous studies, were found to yield highly organised layers on Cu and Ag surfaces by assembly from solution. [62][63][64]73 While it parallels structural features of H3BTC and H3BPTC, its substantially larger size and, thus, more complex geometry raises the question to what extent it exhibits a behaviour along the lines of the smaller analogues.…”

Section: Introductionmentioning

confidence: 99%

Self-assembly of 1,3,5-benzenetribenzoic acid on Ag and Cu at the liquid/solid interface

Aitchison

Morena

et al. 2018

Phys. Chem. Chem. Phys.

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Assembly of 1,3,5-benzenetribenzoic acid (H3BTB) from solution on Au substrates modified by underpotential deposited Ag and Cu layers was studied by near edge X-ray absorption fine structure spectroscopy, X-ray photoelectron spectroscopy and scanning tunneling microscopy. Adsorption of H3BTB on Cu resulted in disordered layers with sporadic occurrence of ordered molecular aggregates. In contrast, highly ordered layers were obtained on Ag which exhibit a pronounced row structure and involve a monopodal bidentate adsorption geometry of the molecules through carboxylate coordinating bonding. The row structure arises from π-stacking of the molecules and is accompanied by hydrogen bonding interactions between the COOH groups of adjacent rows. As a consequence of the geometry of the H3BTB molecule and the dominance of intermolecular over molecule-substrate interactions, the SAM forms an open structure featuring a grooved surface and nanotunnels.

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“…Nevertheless, first steps in that direction have been undertaken and biphenyl-based SAMs on all kinds of substrates have been studied. [72,[80][81][82][83][84][85][86][87][88]60] We, however, do not consider this to be an all too serious problem, as we have high confidence in the employed computational approach, which is described in the following section. This confidence is based on the fact that in the past we have observed an excellent agreement between measured and simulated core-level shifts for a variety of self-assembled monolayers.…”

Section: Introductionmentioning

confidence: 99%

X-Ray Photoelectron Spectroscopy for Determining Interface Dipoles of Self-Assembled Monolayers

Taucher¹,

Zojer²

2020

Preprint

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In the current manuscript we assess to what extent X-ray photoelectron spectroscopy is a suitable tool for probing the dipoles formed at interfaces between self-assembled monolayers and metal substrates. To that aim, we perform dispersion-corrected, slab-type band-structure calculations on a number of biphenyl-based systems bonded to a Au(111) surface via different docking groups. In addition to changing the docking chemistry (and the associated interface dipoles), also the impacts of polar tail-group substituents and varying dipole densities are investigated. We find that for densely-packed monolayers the shifts of the peak positions of the simulated XP-spectra are a direct measure for the interface dipoles. In the absence of polar tail-group substituents they also directly correlate with adsorption-induced work-function changes. At reduced dipole-densities this correlation deteriorates, as work function measurements probe the difference between the Fermi-level of the substrate and the electrostatic energy far above the interface, while core level shifts are determined by the local electrostatic energy in the region of the atom from which the photoelectron is excited.

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Binding groups for highly ordered SAM formation: carboxylic versus thiol

Cited by 26 publications

References 27 publications

Thermally Stable and Highly Conductive SAMs on Ag Substrate—The Impact of the Anchoring Group

Thermally Stable and Highly Conductive SAMs on Ag Substrate—The Impact of the Anchoring Group

Self-assembly of 1,3,5-benzenetribenzoic acid on Ag and Cu at the liquid/solid interface

X-Ray Photoelectron Spectroscopy for Determining Interface Dipoles of Self-Assembled Monolayers

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