Coordination controlled electrodeposition and patterning of layers of palladium/copper nanoparticles on top of a self-assembled monolayer

Zhe She, Zhen Yao, Hervé Ménard, Sven Tobish, Dorothée Lahaye, Neil R. Champness, Manfred Buck (Lead / Corresponding author)

Research output: Contribution to journalArticle

Abstract

A scheme for the generation of bimetallic nanoparticles is presented which combines electrodeposition of one type of metal, coordinated to a self-assembled monolayer (SAM), with another metal deposited from the bulk electrolyte. In this way PdCu nanoparticles are generated by initial complexation of Pd2+ to a SAM of 3-(4-(pyridine-4-yl)phenyl)propane-1-thiol (PyP3) on Au/mica and subsequent reduction in an acidic aqueous CuSO4 electrolyte. Cyclic voltammetry reveals that the onset of Cu deposition is triggered by Pd reduction. Scanning tunneling microscopy (STM) shows that layers of connected particles are formed with an average thickness of less than 3 nm and lateral dimensions of particles in the range of 2 to 5 nm. In X-ray photoelectron spectra a range of binding energies for the Pd 3d signal is observed whereas the Cu 2p signal appears at a single binding energy, even though chemically different Cu species are present: normal and more noble Cu. Up to three components are seen in the N 1s signal, one originating from protonated pyridine moieties, the others reflecting the SAM-metal interaction. It is suggested that the coordination controlled electrodeposition yields layers of particles composed of a Pd core and a Cu shell with a transition region of a PdCu alloy. Deposited on top of the PyP3 SAM, the PdCu particles exhibit weak adhesion which is exploited for patterning by selective removal of particles employing scanning probe techniques. The potential for patterning down to the sub-10 nm scale is demonstrated. Harnessing the deposition contrast between native and PdCu loaded PyP3 SAMs, structures thus created can be developed into patterned continuous layers.
Original languageEnglish
Pages (from-to)13773-13782
Number of pages10
JournalNanoscale
Volume11
Issue number29
Early online date15 Jul 2019
DOIs
Publication statusPublished - 15 Jul 2019

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Palladium
Self assembled monolayers
Electrodeposition
Copper
Nanoparticles
Metals
Binding energy
Pyridine
Electrolytes
Mica
Scanning tunneling microscopy
Photoelectrons
Complexation
Propane
Cyclic voltammetry
Adhesion
Scanning
X rays

Cite this

She, Zhe ; Yao, Zhen ; Ménard, Hervé ; Tobish, Sven ; Lahaye, Dorothée ; Champness, Neil R. ; Buck, Manfred. / Coordination controlled electrodeposition and patterning of layers of palladium/copper nanoparticles on top of a self-assembled monolayer. In: Nanoscale. 2019 ; Vol. 11, No. 29. pp. 13773-13782.
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abstract = "A scheme for the generation of bimetallic nanoparticles is presented which combines electrodeposition of one type of metal, coordinated to a self-assembled monolayer (SAM), with another metal deposited from the bulk electrolyte. In this way PdCu nanoparticles are generated by initial complexation of Pd2+ to a SAM of 3-(4-(pyridine-4-yl)phenyl)propane-1-thiol (PyP3) on Au/mica and subsequent reduction in an acidic aqueous CuSO4 electrolyte. Cyclic voltammetry reveals that the onset of Cu deposition is triggered by Pd reduction. Scanning tunneling microscopy (STM) shows that layers of connected particles are formed with an average thickness of less than 3 nm and lateral dimensions of particles in the range of 2 to 5 nm. In X-ray photoelectron spectra a range of binding energies for the Pd 3d signal is observed whereas the Cu 2p signal appears at a single binding energy, even though chemically different Cu species are present: normal and more noble Cu. Up to three components are seen in the N 1s signal, one originating from protonated pyridine moieties, the others reflecting the SAM-metal interaction. It is suggested that the coordination controlled electrodeposition yields layers of particles composed of a Pd core and a Cu shell with a transition region of a PdCu alloy. Deposited on top of the PyP3 SAM, the PdCu particles exhibit weak adhesion which is exploited for patterning by selective removal of particles employing scanning probe techniques. The potential for patterning down to the sub-10 nm scale is demonstrated. Harnessing the deposition contrast between native and PdCu loaded PyP3 SAMs, structures thus created can be developed into patterned continuous layers.",
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Coordination controlled electrodeposition and patterning of layers of palladium/copper nanoparticles on top of a self-assembled monolayer. / She, Zhe; Yao, Zhen; Ménard, Hervé; Tobish, Sven; Lahaye, Dorothée; Champness, Neil R.; Buck, Manfred (Lead / Corresponding author).

In: Nanoscale, Vol. 11, No. 29, 15.07.2019, p. 13773-13782.

Research output: Contribution to journalArticle

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AU - She, Zhe

AU - Yao, Zhen

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AU - Lahaye, Dorothée

AU - Champness, Neil R.

AU - Buck, Manfred

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N2 - A scheme for the generation of bimetallic nanoparticles is presented which combines electrodeposition of one type of metal, coordinated to a self-assembled monolayer (SAM), with another metal deposited from the bulk electrolyte. In this way PdCu nanoparticles are generated by initial complexation of Pd2+ to a SAM of 3-(4-(pyridine-4-yl)phenyl)propane-1-thiol (PyP3) on Au/mica and subsequent reduction in an acidic aqueous CuSO4 electrolyte. Cyclic voltammetry reveals that the onset of Cu deposition is triggered by Pd reduction. Scanning tunneling microscopy (STM) shows that layers of connected particles are formed with an average thickness of less than 3 nm and lateral dimensions of particles in the range of 2 to 5 nm. In X-ray photoelectron spectra a range of binding energies for the Pd 3d signal is observed whereas the Cu 2p signal appears at a single binding energy, even though chemically different Cu species are present: normal and more noble Cu. Up to three components are seen in the N 1s signal, one originating from protonated pyridine moieties, the others reflecting the SAM-metal interaction. It is suggested that the coordination controlled electrodeposition yields layers of particles composed of a Pd core and a Cu shell with a transition region of a PdCu alloy. Deposited on top of the PyP3 SAM, the PdCu particles exhibit weak adhesion which is exploited for patterning by selective removal of particles employing scanning probe techniques. The potential for patterning down to the sub-10 nm scale is demonstrated. Harnessing the deposition contrast between native and PdCu loaded PyP3 SAMs, structures thus created can be developed into patterned continuous layers.

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