Adsorption geometry, molecular interaction, and charge transfer of triphenylamine-based dye on rutile TiO{sub 2}(110)

Journal Article · Tue Dec 14 00:00:00 EST 2010 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3509389· OSTI ID:21559960

Shun, Yu; Ahmadi, Sareh; Weissenrieder, Jonas; Goethelid, Mats ^[1]; Zuleta, Marcelo ^[2]; Haining, Tian; Xichuan, Yang ^[3]; Schulte, Karina; Pietzsch, Annette; Hennies, Franz ^[4]

---

1. Materials Physics, MAP, ICT, Royal Institute of Technology (KTH), Electrum 229, SE-16440 Kista (Sweden)
2. Physical and Analytical Chemistry Department, Uppsala University, Box 259, SE-75105 Uppsala (Sweden)
3. State Key Laboratory of Fine Chemicals, Dalian University of Technology, Box 46, 158 Zhongshan Rd., Dalian 116012 (China)
4. Max-lab, Lund University, Box 118, S-221 00 Lund (Sweden)

The fast development of new organic sensitizers leads to the need for a better understanding of the complexity and significance of their adsorption processes on TiO{sub 2} surfaces. We have investigated a prototype of the triphenylamine-cyanoacrylic acid (donor-acceptor) on rutile TiO{sub 2} (110) surface with special attention on the monolayer region. This molecule belongs to the type of dye, some of which so far has delivered the record efficiency of 10%-10.3% for pure organic sensitizers [W. Zeng, Y. Cao, Y. Bai, Y. Wang, Y. Shi, M. Zhang, F. Wang, C. Pan, and P. Wang, Chem. Mater. 22, 1915 (2010)]. The molecular configuration of this dye on the TiO{sub 2} surface was found to vary with coverage and adopt gradually an upright geometry, as determined from near edge x-ray absorption fine structure spectroscopy. Due to the molecular interaction within the increasingly dense packed layer, the molecular electronic structure changes systematically: all energy levels shift to higher binding energies, as shown by photoelectron spectroscopy. Furthermore, the investigation of charge delocalization within the molecule was carried out by means of resonant photoelectron spectroscopy. A fast delocalization ({approx}1.8 fs) occurs at the donor part while a competing process between delocalization and localization takes place at the acceptor part. This depicts the ''push-pull'' concept in donor-acceptor molecular system in time scale.

• OSTI ID: 21559960
• Journal Information: Journal of Chemical Physics, Vol. 133, Issue 22; Other Information: DOI: 10.1063/1.3509389; (c) 2010 American Institute of Physics; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
36 MATERIALS SCIENCE
ABSORPTION SPECTROSCOPY
ADSORPTION
BINDING ENERGY
EFFICIENCY
ELECTRONIC STRUCTURE
ENERGY LEVELS
FINE STRUCTURE
INTERACTIONS
MOLECULAR STRUCTURE
PHOTOELECTRON SPECTROSCOPY
RUTILE
SENSITIZERS
SURFACES
TITANIUM OXIDES
X-RAY SPECTROSCOPY
CHALCOGENIDES
ELECTRON SPECTROSCOPY
ENERGY
MATERIALS
MINERALS
OXIDE MINERALS
OXIDES
OXYGEN COMPOUNDS
RADIOACTIVE MATERIALS
RADIOACTIVE MINERALS
REAGENTS
SORPTION
SPECTROSCOPY
TITANIUM COMPOUNDS
TRANSITION ELEMENT COMPOUNDS