X-ray absorption and photoemission spectroscopy of zinc protoporphyrin adsorbed on rutile TiO2(110) prepared by <i>in situ</i> electrospray deposition

Rienzo, Anna Maria Di; Mayor, Louise C.; Magnano, Graziano; Satterley, Christopher J.; Ataman, Evren; Schnadt, Joachim; Schulte, Karina; O’Shea, James N.

doi:10.1063/1.3336747

Cited by 55 publications

(92 citation statements)

References 35 publications

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“…In potassium doped ZnPc films it was shown that although the HOMO/LUMO shifted by 0.6 eV with respect to the Fermi level, Zn3d remained at the same position. In our case, the different shifts in Zn3d, C1s and N1s are a combined result of 1) the loss of electrons in the molecule mainly affects the inner ring of the molecule 28 put zinc protoporphyrin on TiO 2 , which has a similar molecular structure as ZnPc, and observed a removal of the zinc atom from the central porphyrin ring. This resulted in a Zn2p shift to lower binding energy compared the thick film, indicating a more neutral zinc atom on the surface.…”

Section: Photoelectron Spectroscopymentioning

confidence: 96%

Inhomogeneous charge transfer within monolayer zinc phthalocyanine absorbed on TiO2(110)

Ahmadi

Sun

et al. 2012

The Journal of Chemical Physics

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Adsorption geometry, molecular interaction, and charge transfer of triphenylamine-based dye on rutile TiO2 (110) The d-orbital contribution from the transition metal centers of phthalocyanine brings difficulties to understand the role of the organic ligands and their molecular frontier orbitals when it adsorbs on oxide surfaces. Here we use zinc phthalocyanine (ZnPc)/TiO 2 (110) as a model system where the zinc d-orbitals are located deep below the organic orbitals leaving room for a detailed study of the interaction between the organic ligand and the substrate. A charge depletion from the highest occupied molecular orbital is observed, and a consequent shift of N1s and C1s to higher binding energy in photoelectron spectroscopy (PES). A detailed comparison of peak shifts in PES and near-edge X-ray absorption fine structure spectroscopy illustrates a slightly uneven charge distribution within the molecular plane and an inhomogeneous charge transfer screening between the center and periphery of the organic ligand: faster in the periphery and slower at the center, which is different from other metal phthalocyanine, e.g., FePc/TiO 2 . Our results indicate that the metal center can substantially influence the electronic properties of the organic ligand at the interface by introducing an additional charge transfer channel to the inner molecular part.

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Section: Photoelectron Spectroscopymentioning

confidence: 96%

Inhomogeneous charge transfer within monolayer zinc phthalocyanine absorbed on TiO2(110)

Ahmadi

Sun

et al. 2012

The Journal of Chemical Physics

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“…9,13 The average orientation of adsorbed molecules relative to the surface could be derived from combined near-edge x-ray absorption fine structure spectroscopy (NEXAFS) and photoelectron spectroscopy (PES). [14][15][16] However, the irregular mesoporous titania surface prevents averaging techniques from capturing 4 local molecular details. Scanning probe techniques can in principle overcome this difficulty and provide direct, local information about the adsorbed layer.…”

Section: Introductionmentioning

confidence: 99%

In Situ Mapping of the Molecular Arrangement of Amphiphilic Dye Molecules at the TiO₂ Surface of Dye-Sensitized Solar Cells

Voïtchovsky

Astani

Tavernelli

et al. 2015

ACS Appl. Mater. Interfaces

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Citation for published item:o¤ %t hovskyD uF nd esh ri est niD xF nd vernelliD sF nd etre ultD xF nd othlis ergerD F nd tell iD pF nd qr¤ tzelD wF nd erne r rmsD rF @PHISA 9snEsitu m pping of the mole ul r rr ngement of mphiphili dye mole ules t the iyP surf e of dye sensitized sol r ellsF9D eg pplied m teri ls interf esFD U @PHAF ppF IHVQREIHVRPF Further information on publisher's website: httpXGGdxFdoiForgGIHFIHPIG s miFS HITQV Publisher's copyright statement: This document is the Accepted Manuscript version of a Published Work that appeared in nal form in ACS applied materials interfaces, copyright c 2015 American Chemical Society after peer review and technical editing by the publisher. To access the nal edited and published work see http://dx.doi.org/10.1021/acsami.5b01638. Additional information:Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. Just Accepted "Just Accepted" manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides "Just Accepted" as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. "Just Accepted" manuscripts appear in full in PDF format accompanied by an HTML abstract. "Just Accepted" manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). "Just Accepted" is an optional service offered to authors. Therefore, the "Just Accepted" Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the "Just Accepted" Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these "Just Accepted" manuscripts. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59

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“…18 This electronic effect on the surface Ti atoms is further enhanced upon the formation of a (1 Â 2) surface reconstruction, induced by high-temperature annealing. 19 Very recently, the strong structural anisotropy of the TiO 2 -(110) surface has been tentatively exploited as a template to drive the oriented growth of planar organic molecules, such as phthalocyanines, [20][21][22] porphyrins, 23 and perylene derivatives. [24][25][26] When these molecules adsorb flat onto the substrate, the intralayer lateral transport is inhibited, but a much faster charge transfer to the substrate has been reported.…”

Section: Introductionmentioning

confidence: 99%

Planar Growth of Pentacene on the Dielectric TiO₂(110) Surface

Lanzilotto

Sánchez‐Sánchez

Bavdek³

et al. 2011

J. Phys. Chem. C

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We have studied the growth of pentacene molecules on the unreconstructed and stoichiometric surface of TiO2(110). At variance with its characteristic homeotropic growth mode, pentacene is found to be physisorbed on this dielectric substrate with its long molecular axis oriented parallel to the surface and aligned along the [001] direction. Pentacene molecules couple side-by-side into long stripes running along the [11̅0] direction, where the overlayer preserves the substrate lattice periodicity (∼6.5 Å). In the opposite direction, head-to-head pentacene repulsion drives the ordering of the stripes, whose spacing simply depends on the surface coverage. By near-edge X-ray absorption, NEXAFS, we have determined the pentacene molecules to be tilted by ∼25° off the surface around their long axis. At the monolayer coverage, the pentacene orientation and spacing are very close to that of the (010) bulk planes (also called a−c planes) of pentacene crystals. We have observed that at least two additional layers can be grown on top of the monolayer following a planar configuration. Both the strong side-by-side intermolecular attraction and the full development of the bulklike electronic states, as probed by NEXAFS, suggest an optimal charge transport along the monolayer stripes of lying-down molecules.

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X-ray absorption and photoemission spectroscopy of zinc protoporphyrin adsorbed on rutile TiO2(110) prepared by in situ electrospray deposition

Cited by 55 publications

References 35 publications

Inhomogeneous charge transfer within monolayer zinc phthalocyanine absorbed on TiO2(110)

Inhomogeneous charge transfer within monolayer zinc phthalocyanine absorbed on TiO2(110)

In Situ Mapping of the Molecular Arrangement of Amphiphilic Dye Molecules at the TiO₂ Surface of Dye-Sensitized Solar Cells

Planar Growth of Pentacene on the Dielectric TiO₂(110) Surface

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X-ray absorption and photoemission spectroscopy of zinc protoporphyrin adsorbed on rutile TiO2(110) prepared by in situ electrospray deposition

Cited by 55 publications

References 35 publications

Inhomogeneous charge transfer within monolayer zinc phthalocyanine absorbed on TiO2(110)

Inhomogeneous charge transfer within monolayer zinc phthalocyanine absorbed on TiO2(110)

In Situ Mapping of the Molecular Arrangement of Amphiphilic Dye Molecules at the TiO2 Surface of Dye-Sensitized Solar Cells

Planar Growth of Pentacene on the Dielectric TiO2(110) Surface

Contact Info

Product

Resources

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In Situ Mapping of the Molecular Arrangement of Amphiphilic Dye Molecules at the TiO₂ Surface of Dye-Sensitized Solar Cells

Planar Growth of Pentacene on the Dielectric TiO₂(110) Surface