Adsorption of a Ru(II) dye complex on the Au(111) surface: Photoemission and scanning tunneling microscopy

Mayor, Louise C.; Saywell, Alex; Magnano, Graziano; Satterley, Christopher J.; Schnadt, Joachim; O’Shea, James N.

doi:10.1063/1.3122685

Cited by 25 publications

(39 citation statements)

References 26 publications

(40 reference statements)

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“…pMS could be of great importance to other surface science analysis instruments such as synchrotron sources (141) or electron microscopes (107,108). Standardized commercial solutions for pMS/SPM do not exist and are not likely to appear in the near future.…”

Section: Discussionmentioning

confidence: 99%

Mass Spectrometry as a Preparative Tool for the Surface Science of Large Molecules

Rauschenbach

Ternes

Harnau

et al. 2016

Annual Rev. Anal. Chem.

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Measuring and understanding the complexity that arises when nanostructures interact with their environment are one of the major current challenges of nanoscale science and technology. High-resolution microscopy methods such as scanning probe microscopy have the capacity to investigate nanoscale systems with ultimate precision, for which, however, atomic scale precise preparation methods of surface science are a necessity. Preparative mass spectrometry (pMS), defined as the controlled deposition of m/z filtered ion beams, with soft ionization sources links the world of large, biological molecules and surface science, enabling atomic scale chemical control of molecular deposition in ultrahigh vacuum (UHV). Here we explore the application of high-resolution scanning probe microscopy and spectroscopy to the characterization of structure and properties of large molecules. We introduce the fundamental principles of the combined experiments electrospray ion beam deposition and scanning tunneling microscopy. Examples for the deposition and investigation of single particles, for layer and film growth, and for the investigation of electronic properties of individual nonvolatile molecules show that state-of-the-art pMS technology provides a platform analog to thermal evaporation in conventional molecular beam epitaxy. Additionally, it offers additional, unique features due to the use of charged polyatomic particles. This new field is an enormous sandbox for novel molecular materials research and demands the development of advanced molecular ion beam technology.

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Section: Discussionmentioning

confidence: 99%

Mass Spectrometry as a Preparative Tool for the Surface Science of Large Molecules

Rauschenbach

Ternes

Harnau

et al. 2016

Annual Rev. Anal. Chem.

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“…Peak assignment also agrees with previously published data. 16 No change in energy of the C 1s peaks related to pyridine and thiocyanate was observed. These parts are in the same chemical environment in both the monolayer and multilayer, which indicates that these parts of the molecule are not involved in bonding to the surface.…”

Section: A Adsorption Bondingmentioning

confidence: 99%

“…16,18 The dye molecule was dissolved in a solution of 3(methanol):1(water) and sprayed for 90 min during which the pressure rose to 2 × 10 −7 mbar due to gas load from the electrospray system and the presence of solvent molecules in the molecule beam. This formed a deposition spot on the surface a few millimeters in diameter with a range of coverages in a Gaussian distribution, from partial monolayer at the edges to multilayer in the centre.…”

Section: Methodsmentioning

confidence: 99%

“…Prior research of N3 on Au(111) the bonding is dominated by the sulphur atom on the thiocyanate and van der Waals forces from the remainder of the molecule. 16 On TiO 2 N3 has shown bonding via de-protonation of two carboxylic acid groups on the bi-isonicotinic acid ligand, and via the interaction of sulphur on the thiocyanate ligand. 17 Since the surface in this experiment is oxygen terminated it is expected that N3 will form chemical bonds with the surface in a manner similar to that seen on TiO 2 .…”

Section: Introductionmentioning

confidence: 99%

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Charge transfer from an adsorbed ruthenium-based photosensitizer through an ultra-thin aluminium oxide layer and into a metallic substrate

Gibson

Temperton

Handrup

et al. 2014

The Journal of Chemical Physics

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The version presented here may differ from the published version or from the version of record. If you wish to cite this item you are advised to consult the publisher's version. Please see the repository url above for details on accessing the published version and note that access may require a subscription. The interaction of the dye molecule N3 (cis-bis(isothiocyanato)bis(2,2-bipyridyl-4,4 -dicarboxylato)-ruthenium(II)) with the ultra-thin oxide layer on a AlNi(110) substrate, has been studied using synchrotron radiation based photoelectron spectroscopy, resonant photoemission spectroscopy, and near edge X-ray absorption fine structure spectroscopy. Calibrated X-ray absorption and valence band spectra of the monolayer and multilayer coverages reveal that charge transfer is possible from the molecule to the AlNi(110) substrate via tunnelling through the ultra-thin oxide layer and into the conduction band edge of the substrate. This charge transfer mechanism is possible from the LUMO+2 and 3 in the excited state but not from the LUMO, therefore enabling core-hole clock analysis, which gives an upper limit of 6.0 ± 2.5 fs for the transfer time. This indicates that ultra-thin oxide layers are a viable material for use in dye-sensitized solar cells, which may lead to reduced recombination effects and improved efficiencies of future devices. © 2014 AIP Publishing LLC.

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“…This technique has been used successfully in previous studies to deposit carbon nanotubes, 18 C 60 molecules, 19,20 zinc protoporphyrin, 21 polymers, 22 biomolecules, 23 and the Ru 535 dye complex. 9,24 The adsorbed dye molecules were studied using Xray photoemission spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, and resonant photoemission spectroscopy (RPES) in order to observe their bonding, electronic structure, and charge transfer dynamics.…”

Section: Introductionmentioning

confidence: 99%

Charge transfer dynamics of model charge transfer centers of a multicenter water splitting dye complex on rutile TiO2(110)

Weston

Britton

O’Shea

2011

The Journal of Chemical Physics

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Charge transfer dynamics between an adsorbed molecule and a rutile TiO(2)(110) surface have been investigated in three organometallic dyes related to multicenter water splitting dye complexes: Ru 535 (cis-bis(isothiocyanato)bis(2,2'-bipyridyl-4,4'-dicarboxylato)-ruthenium(II)), Ru 455 (cis-bis(2,2'-bipyridyl)-(2,2'-bipyridyl-4,4'-dicarboxylic acid)-ruthenium(II)), and Ru 470 (tris(2,2'-bipyridyl-4,4'-dicarboxylic acid)-ruthenium(II)). The adsorption of the dye molecules on the rutile TiO(2)(110) surface has been studied using core-level and valence photoemission. Dye molecules were deposited in situ using ultrahigh vacuum electrospray deposition. Core-level photoemission spectra reveal that each complex bonds to the surface via deprotonation of two carboxylic groups. All three dye complexes show evidence of ultrafast charge transfer to the TiO(2) substrate using the core-hole clock implementation of resonant photoemission spectroscopy.

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Adsorption of a Ru(II) dye complex on the Au(111) surface: Photoemission and scanning tunneling microscopy

Cited by 25 publications

References 26 publications

Mass Spectrometry as a Preparative Tool for the Surface Science of Large Molecules

Mass Spectrometry as a Preparative Tool for the Surface Science of Large Molecules

Charge transfer from an adsorbed ruthenium-based photosensitizer through an ultra-thin aluminium oxide layer and into a metallic substrate

Charge transfer dynamics of model charge transfer centers of a multicenter water splitting dye complex on rutile TiO2(110)

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