Metallization of Ultra‐Thin, Non‐Thiol SAMs with Flat‐Lying Molecular Units: Pd on 1, 4‐Dicyanobenzene

Eberle, Felix; Metzler, Martin; Kolb, Dieter M.; Saitner, Marc; Wagner, Patrick; Boyen, Hans‐Gerd

doi:10.1002/cphc.201000309

Cited by 14 publications

(11 citation statements)

References 46 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Taking into account the dimension of the 2-MBT molecule [44], we can deduce that 2-MBT in the monolayer adsorbs with its plane almost parallel to the sample surface. This is consistent with the fact that S-containing molecules can adsorb on metallic surface with small tilt angle [45,46].…”

Section: Thickness Of the 2-mbt Layerssupporting

confidence: 88%

2-Mercaptobenzothiazole corrosion inhibitor deposited at ultra-low pressure on model copper surfaces

Wiame

Maurice

et al. 2020

Corrosion Science

View full text Add to dashboard Cite

Adsorption of 2-mercaptobenzothiazole (2-MBT) at ultra-low pressure and room temperature on metallic and pre-oxidized Cu(111) surfaces and its thermal stability were investigated using X-ray photoelectron spectroscopy in order to better understand the interfacial corrosion inhibiting properties. 2-MBT is lying flat in the monolayer with two sulphur atoms bonded to Cu and decomposes partially yielding atomic sulphur when interacting with metallic copper prior to forming molecular multilayers. Decomposition is prevented by surface pre-oxidation with 2D oxide dissociation accelerating the 2-MBT initial adsorption kinetics. 2-MBT further decomposes and partially desorbs above 100 • C. A pre-adsorbed 2-MBT monolayer on metallic copper inhibits surface corrosion. sulphur in the organic molecule could improve its capacity as corrosion inhibitor by forming coordinative bonds with copper [1]. It has been shown that 2-MBT dissolved in solution can react with copper to form a complex which acts as a protective layer at the copper surface [21]. However, controversy exists on the chemical nature of the complex formed, as well as on the fundamental mechanisms of the inhibiting interaction. The resulting structures of the protective layer formed on copper are also still not clear. Most notably, the exact role of the surface oxide in the inhibiting function remains to be studied. With few exceptions [12], experimental research concerning corrosion inhibitors have been done by immersion into solutions containing the organic compounds [7-24]. However, in order to elucidate the interaction mechanisms, deposition of the molecule evaporated in vacuum could be more insightful, since it allows controlling each step of the deposition process in a well-defined environment and on a well-defined surface. Data have been reported for vacuum evaporation [25, 26] of 1,4-benzenedimethanethiol (BDMT) on Au(111), Au(110), Cu(100) and Cu(111) single crystal surfaces. The authors found that on Cu (100) and Cu(111) surfaces, which are more reactive, BDMT dissociates in the initial stage of adsorption, resulting in atomic S adsorbed on the Cu surface. This phenomenon was not observed for the adsorption of benzotriazole on Cu(100) [27].In this work, the adsorption of 2-MBT at ultra-low pressure (ULP) and room temperature on clean and pre-oxidized Cu(111) surfaces and its effect on the oxidation of copper were investigated using ultra-high vacuum (UHV) spectroscopic techniques. The results were compared to those obtained for ULP deposition on the oxide-covered Cu(111) surface prepared in air. The thermal stability of the adsorbed molecular layer under UHV was also studied. This work brings new insight into the interaction of 2-MBT with copper, which allow us to better understand its corrosion inhibition mechanisms. Material and methodsA high purity (99.999%) Cu(111) single-crystal was used in this work. The surface was mechanically polished to 1/4 µm (diamond paste), successively rinsed with acetone, ethanol, and ultra pure (UP) water (resistivity > 18...

show abstract

Section: Thickness Of the 2-mbt Layerssupporting

confidence: 88%

2-Mercaptobenzothiazole corrosion inhibitor deposited at ultra-low pressure on model copper surfaces

Wiame

Maurice

et al. 2020

Corrosion Science

View full text Add to dashboard Cite

show abstract

“…They also showed that the location of the functional group to which the metal ion coordinates plays an important role, metallization not happening when the functional group is not facing the electrolyte, as in the case of 2-MP [27]. Metallization of a completely different SAM, formed by flat shaped 1,4-dicyanobenzene on Au(111) electrodes was also demonstrated [30], proving that the method is effective as long as irreversible coordination of a metal cation to a suitable functionality is possible. Successful electrochemical metallization of SAMs using the same procedure was subsequently reported by other groups using different metals and SAMs [31][32][33][34], proving the viability and effectiveness of the method.…”

Section: M M Metallization Etallization Etallization Etallization Omentioning

confidence: 95%

Electrochemical metallization of molecular adlayers

Mwanda

Cuesta

2019

Current Opinion in Electrochemistry

View full text Add to dashboard Cite

Electrochemical metallization of molecular adlayers allows to sandwich a group of molecules between a metallic substrate and a metal nanoisland or nanocluster through a wet process not requiring expensive vacuum equipment and with precise control through the electrode potential. This metal-molecule-metal sandwiches could provide a simple means to integrate molecules in electronic circuits, or to explore effects arising due to quantum confinement of electrons due to the reduced dimensions of the islands or clusters deposited on the adlayer. Although initial attempts resulted in penetration through the adlayer and direct deposition on the metal substrate, the development 14 years ago of a two-step technique involving preadsorption of the target cation on the SAM prior to its reduction in an electrolyte not containing that cation opened a whole new range of possibilities. In this brief review we discuss the development and recent advances in the implementation of this technique, and briefly discuss the outlook for future work.

show abstract

“…Later, we have reported a method to make a metal-SAM-metal structure more suitable for the application in electronic nano-devices and measurements of charge transport property through organic molecules by using dithiol SAMs, 1,4-benzenedimethanethiol (BDMT) or hexanedithiol (HDT), in which free thiol head groups provide stronger interaction between top metal and the SAM [4,5,[13][14][15], and a symmetric coupling in metal-molecule-metal junction was formed [44,45]. More recently, Kolb and co-workers reported that Pd can be deposited on thiazole [46] and flat lying 1,4-dicyanobenzene SAMs [47].…”

Section: Introductionmentioning

confidence: 98%

Formation of continuous platinum layer on top of an organic monolayer by electrochemical deposition followed by electroless deposition

Uosaki

2011

Journal of Electroanalytical Chemistry

View full text Add to dashboard Cite

Metallization of Ultra‐Thin, Non‐Thiol SAMs with Flat‐Lying Molecular Units: Pd on 1, 4‐Dicyanobenzene

Cited by 14 publications

References 46 publications

2-Mercaptobenzothiazole corrosion inhibitor deposited at ultra-low pressure on model copper surfaces

2-Mercaptobenzothiazole corrosion inhibitor deposited at ultra-low pressure on model copper surfaces

Electrochemical metallization of molecular adlayers

Formation of continuous platinum layer on top of an organic monolayer by electrochemical deposition followed by electroless deposition

Contact Info

Product

Resources

About