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ABSTRACT: We use photoelectron spectroscopy, low energy electron diffraction, scanning tunneling microscopy, and density functional theory to investigate coverage dependent iodine structures on Pd(110). At 0.5 ML (monolayer), a c(2 × 2) structure is formed with iodine occupying the four-fold hollow site. At increasing coverage, the iodine layer compresses into a quasi-hexagonal structure at 2∕3 ML, with iodine occupying both hollow and long bridge positions. There is a substantial difference in electronic structure between these two iodine sites, with a higher electron density on the bridge bonded iodine. In addition, numerous positively charged iodine near vacancies are found along the domain walls. These different electronic structures will have an impact on the chemical properties of these iodine atoms within the layer.
The Journal of chemical physics 11/2012; 137(20):204703. · 3.09 Impact Factor
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ABSTRACT: We have studied zinc phthalocyanine (ZnPc) and iron phthalocyanine (FePc) thick films and monolayers on Au(111) using photoelectron spectroscopy and x-ray absorption spectroscopy. Both molecules are adsorbed flat on the surface at monolayer. ZnPc keeps this orientation in all investigated coverages, whereas FePc molecules stand up in the thick film. The stronger inter-molecular interaction of FePc molecules leads to change of orientation, as well as higher conductivity in FePc layer in comparison with ZnPc, which is reflected in thickness-dependent differences in core-level shifts. Work function changes indicate that both molecules donate charge to Au; through the π-system. However, the Fe3d derived lowest unoccupied molecular orbital receives charge from the substrate when forming an interface state at the Fermi level. Thus, the central atom plays an important role in mediating the charge, but the charge transfer as a whole is a balance between the two different charge transfer channels; π-system and the central atom.
The Journal of chemical physics 08/2012; 137(8):084705. · 3.09 Impact Factor
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ABSTRACT: Photoinduced molecular rearrangements are important in daily events essential for life such as visual perception and photo-protection of light harvesting complexes in plants. In this study we demonstrate that similar photoarrangements appear in an analogous technological application where the device performance is controlled by chromophores in sensitized anatase TiO(2), one of the main components for light-harvesting in dye-sensitized solar cells (DSC). STM reveals that illumination leads to distortions of organic dyes containing conjugated backbones and of cis-bis(isothiocyanate)-bis-(2,2'-bipyridyl-4,4'-dicarboxylate)ruthenium(II)-bis(tetrabutylammonium), known as N719. The dyes were adsorbed in a closed-packed mode on an anatase(101) single crystal surface and imaged in the dark and under white light illumination in an ultra-high vacuum (UHV). STM images of N719 clearly suggest rearrangements caused by rotation of the dye. Conversely, organic dyes rearrange by photoisomerization depending on the number of double bonds, their position in the molecular structure and on the ligand modifications.
Physical Chemistry Chemical Physics 08/2012; 14(30):10780-8. · 3.57 Impact Factor
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ABSTRACT: 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.
The Journal of chemical physics 04/2012; 136(15):154703. · 3.09 Impact Factor
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ABSTRACT: Organic semiconductors usually demonstrate crystal structure dependent electronic properties, and through precise control of film structure, the performance of novel organic electronic devices can be greatly improved. Understanding the crystal structure dependent charge-transfer mechanism thus becomes critical. In this work, we have prepared amorphous titanyl phthalocyanine films by vacuum molecular beam evaporation and have further crystallized them through vacuum annealing. In the crystalline phase, an excited electron is rapidly transferred into neighboring molecules; while in the amorphous phase, it is mainly localized and recombines with the core hole as revealed by resonant photoemission spectroscopy (RPES). The fast electron transfer time is determined to be around 16 fs in the crystalline film, which is in good agreement with the charge-transfer hopping time estimated from the best device performance reported. The crystallized film shows more p-type characteristics than the amorphous with all the energy levels shifting toward the vacuum level. However, the greatly improved charge transfer is assigned to the molecular orbital coupling rather than this shift. From density functional theory and RPES, we specify the contribution of two differently coordinated nitrogen atoms (N2c and N3c) to the experimental results and illustrate that the N3c related orbital has experienced a dramatic change, which is keenly related to the improved charge transfer.
07/2011;
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01/2011;
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ABSTRACT: 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(2) surfaces. We have investigated a prototype of the triphenylamine-cyanoacrylic acid (donor-acceptor) on rutile TiO(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(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 (∼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.
The Journal of chemical physics 12/2010; 133(22):224704. · 3.09 Impact Factor
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ABSTRACT: We report experimental results concerning the STM imaging of cis-bis (isothiocyanate)-bis-(2,2'-bipyridyl-4,4'dicarboxylate)ruthenium(II)bis(tetrabutylammonium) dye (known as N719) adsorbed on a single crystal of anatase TiO(2)(100). The cleaning pretreatment, by sputtering and annealing, of TiO(2)(100) yields a reproducible (1 x n) surface reconstruction. Previous to dye deposition, TiO(2) was covered with one monolayer of 4-tert-butylpyridine (4-TBP) in ultrahigh vacuum (UHV) in order to protect the surface against air contamination. N719 was subsequently deposited by dipping the crystal into the dye solution. 4-TBP was removed partially in the solution and totally by heating the sample to around 285-300 degrees C in UHV. The images of the deposited 4-TBP on TiO(2)(100) revealed a complete surface coverage showing three modes of adsorption on TiO(2). The relatively uncomplicated desorption of 4-TBP enables the accommodation and chemisorption of most N719 molecules directly onto the TiO(2) surface. The STM imaging of N719 was affected, in a reversible way, by illumination, because the quality of the image changed after a few hours in the dark or under illumination conditions. The results presented herein are discussed in terms of changes in molecular configurations and in open circuit potentials.
Langmuir 08/2010; 26(16):13236-44. · 4.19 Impact Factor
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ABSTRACT: In the present work, we study the bonding of 4-tert-butyl pyridine (4TBP) to the TiO2(110) surface using photoelectron spectroscopy (PES) and density functional theory (DFT) calculations. The results show that at low coverage, 4TBP adsorbs preferentially on oxygen vacancies. The calculated adsorption energy at the vacancies is 120 kJ/mol larger than that on the five-fold-coordinated Ti4+ sites located in the rows on the TiO2 surface. The vacancy is “healed” by 4TBP, and the related gap state is strongly reduced through charge transfer into empty π* orbitals on the pyridine ring. This leads to a change in surface band bending by 0.2 eV toward lower binding energies. The band bending does not change with further 4TBP deposition when saturating the surface to monolayer coverage, where the TiO2 surface is effectively protected against further adsorption by the dense 4TBP layer.
01/2010;
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ABSTRACT: Adsorption of titanyl phthalocyanine (TiOPc) on rutile TiO2(110) modified by a set of pyridine derivatives (2,2′-bipyridine, 4,4′-bipyridine, and 4-tert-butyl pyridine) has been investigated using synchrotron radiation based X-ray photoelectron spectroscopy (XPS). For the unmodified TiOPc/TiO2 system, a strong charge transfer is observed from the first layer TiOPc into the substrate, which leads to a molecular layer at the interface with a depleted highest occupied molecular orbital (HOMO). However, precovering the TiO2 surface with a saturated pyridine monolayer effectively reduce this process and leave the TiOPc in a less perturbed molecular state. Furthermore, the TiOPc HOMO and core levels are observed at different binding energies ranging by 0.3 eV on the three pyridine monolayers, which is ascribed to differences in surface potentials set up by the different pyridine/TiO2 systems.
06/2009;
