uu.seUppsala University Publications
Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Dye-sensitization of the TiO2 rutile (110) surface by perylene dyes: Quantum-chemical periodic B3LYP computations
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical Chemistry, Quantum Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical Chemistry, Quantum Chemistry.
2007 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 111, no 32, 12116-12123 p.Article in journal (Refereed) Published
Abstract [en]

The adsorption of perylene derivatives on the rutile TiO2(110) surface was studied by quantum-chemical periodic calculations employing the hybrid HF-DFT functional B3LYP. The perylene molecule, which is a possible constituent of dyes in dye-sensitized solar cells, was functionalized by attachment of phosphonic acid or carboxylic acid groups to permit anchoring to the metal oxide surface. The anchor groups were bound to the molecule directly or via different spacer groups, namely --CH2-, -CH2-CH2-, and -CH = CH-. The effects of the anchor and spacer groups on the adsorption geometry and energy, on the electronic structure of the dye-TiO2 interface, and on the electron transfer rates were investigated. The phosphonic acid anchor group was found to bind the perylene derivatives much more strongly to the surface than the carboxylic acid anchor group. The spacer groups were capable of significantly altering electron transfer rates across the dye-metal oxide interface, where the unsaturated groups permitted injection times in the low femtosecond regime.

Place, publisher, year, edition, pages
2007. Vol. 111, no 32, 12116-12123 p.
National Category
Chemical Sciences Physical Sciences
Identifiers
URN: urn:nbn:se:uu:diva-95558DOI: 10.1021/jp072253lISI: 000248658600054OAI: oai:DiVA.org:uu-95558DiVA: diva2:169821
Available from: 2007-03-01 Created: 2007-03-01 Last updated: 2011-01-29Bibliographically approved
In thesis
1. Computational Investigation of Dye-Sensitized Solar Cells
Open this publication in new window or tab >>Computational Investigation of Dye-Sensitized Solar Cells
2007 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Interfaces between semiconductors and adsorbed molecules form a central area of research in surface science, occurring in many different contexts. One such application is the so-called Dye-Sensitized Solar Cell (DSSC) where the nanostructured dye-semiconductor interface is of special interest, as this is where the most important ultrafast electron transfer process takes place. In this thesis, structural and electronic aspects of these interfaces have been studied theoretically using quantum chemical computations applied to realistic dye-semiconductor systems. Periodic boundary conditions and large cluster models have been employed together with hybrid HF-DFT functionals in the modeling of nanostructured titanium dioxide.

A study of the adsorption of a pyridine molecule via phosphonic and carboxylic acid anchor groups to an anatase (101) surface showed that the choice of anchor group affects the strength of the bindings as well as the electronic interaction at the dye-TiO2 interface. The calculated interfacial electronic coupling was found to be stronger for carboxylic acid than for phosphonic acid, while phosphonic acid binds significantly stronger than carboxylic acid to the TiO2 surface.

Atomistic and electronic structure of realistic dye-semiconductor interfaces were reported for RuII-bis-terpyridine dyes on a large anatase TiO2 cluster and perylene dyes on a periodic rutile (110) TiO2 surface. The results show strong influence of anchor and inserted spacer groups on adsorption and electronic properties. Also in these cases, the phosphonic acid anchor group was found to bind the dyes significantly stronger to the surface than the carboxylic acid anchor, while the interfacial electronic coupling was stronger for the carboxylic anchor. The estimated electron injection times were twice as fast for the carboxylic anchor compared to the phosphonic anchor. Moreover, the electronic coupling was affected by the choice of spacer group, where unsaturated spacer groups were found to mediate electron transfer more efficiently than saturated ones.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2007. 70 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 281
Keyword
Quantum chemistry, titanium dioxide, anatase, rutile, pyridine, perylene, nanostructured, interface, electronic coupling, electron injection, quantum chemistry, phosphonic acid, Kvantkemi
Identifiers
urn:nbn:se:uu:diva-7673 (URN)978-91-554-6820-0 (ISBN)
Public defence
2007-03-23, Häggsalen, The Ångström Laboratory, Lägerhyddsvägen 1, Uppsala, 13:15
Opponent
Supervisors
Available from: 2007-03-01 Created: 2007-03-01 Last updated: 2010-06-09Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full text
By organisation
Quantum Chemistry
In the same journal
The Journal of Physical Chemistry C
Chemical SciencesPhysical Sciences

Search outside of DiVA

GoogleGoogle Scholar

doi
urn-nbn

Altmetric score

doi
urn-nbn
Total: 971 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf