| 1. |
- Ahmadi, Sareh, et al.
(författare)
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Site-dependent charge transfer at the Pt(111)-ZnPc interface and the effect of iodine
- 2014
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Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 140:17, s. 174702-
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Tidskriftsartikel (refereegranskat)abstract
- The electronic structure of ZnPc, from sub-monolayers to thick films, on bare and iodated Pt(111) is studied by means of X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and scanning tunneling microscopy. Our results suggest that at low coverage ZnPc lies almost parallel to the Pt(111) substrate, in a non-planar configuration induced by Zn-Pt attraction, leading to an inhomogeneous charge distribution within the molecule and an inhomogeneous charge transfer to the molecule. ZnPc does not form a complete monolayer on the Pt surface, due to a surface-mediated intermolecular repulsion. At higher coverage ZnPc adopts a tilted geometry, due to a reduced molecule-substrate interaction. Our photoemission results illustrate that ZnPc is practically decoupled from Pt, already from the second layer. Pre-deposition of iodine on Pt hinders the Zn-Pt attraction, leading to a non-distorted first layer ZnPc in contact with Pt(111)-I(root 3x root 3) or Pt(111)-I(root 7x root 7), and a more homogeneous charge distribution and charge transfer at the interface. On increased ZnPc thickness iodine is dissolved in the organic film where it acts as an electron acceptor dopant.
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| 2. |
- Bidermane, Ieva, 1984-, et al.
(författare)
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Adsorption and Molecular Orientation of Lutetium bi-Phthalocyanine Adlayers on Pristine Si(100)2x1 Surface
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- A combined photoelectron spectroscopy (PES), X-ray absorption spectroscopy (XAS)and scanning tunneling microscopy (STM) study has been performed to follow thechange in adsorption geometry and to characterize the adsorbate interaction with thesubstrate for dierent thicknesses of lutetium biphthalocyanine (LuPc2) adlayers onpristine Si(100)-2x1 reconstructed stepped surface. A shift to lower binding energieswith increasing thickness has been shown. The STM results showed clustering ofLuPc2 starting from submonolayer coverages and two distinct adsorption types havebeen identied. The STM and PES results have been linked together to propose twodierent adsorption types involving a stronger and weaker interaction with the Sidangling bonds. A change in average angle of molecules with respect to the normalof the surface for increasing thicknesses has been seen from the XAS measurements,leading to disordered layers for thicker films.
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| 3. |
- Bidermane, Ieva, 1984-, et al.
(författare)
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Atomic Contributions to the Valence Band Photoelectron Spectra of Metal-free, Iron and Manganese Phthalocyanines
- 2015
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Ingår i: Journal of Electron Spectroscopy and Related Phenomena. - : Elsevier BV. - 0368-2048 .- 1873-2526. ; 205, s. 92-97
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Forskningsöversikt (övrigt vetenskapligt/konstnärligt)abstract
- The present work reports a photoelectron spectroscopy study of the low-energy region of the valence band of metal-free phthalocyanine (H2Pc) compared with those of iron phthalocyanine (FePc) and manganese phthalocyanine (MnPc). We have analysed in detail the atomic orbital composition of the valence band both experimentally, by making use of the variation in photoionization cross-sections with photon energy, and theoretically, by means of density functional theory. The atomic character of the Highest Occupied Molecular Orbital (HOMO), reflected on the outermost valence band binding energy region, is different for MnPc as compared to the other two molecules. The peaks related to the C 2p contributions, result in the HOMO for H2Pc and FePc and in the HOMO-1 for MnPc as described by the theoretical predictions, in very good agreement with the experimental results. The DFT simulations, discerning the atomic contribution to the density of states, indicate how the central metal atom interacts with the C and N atoms of the molecule, giving rise to different partial and total density of states for these three Pc molecules.
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| 4. |
- Bidermane, Ieva, 1984-, et al.
(författare)
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Characterization of Gas Phase of Iron Phthalocyanine with X-ray Photoelectron and Absorption Spectroscopies
- 2015
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Ingår i: Physica status solidi. B, Basic research. - : Wiley. - 0370-1972 .- 1521-3951. ; 252:6, s. 1259-1265
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Tidskriftsartikel (refereegranskat)abstract
- Despite the numerous studies dedicated to phthalocyanine molecules adsorbed on surfaces, in monolayer or thin film, very few works have been focused on the characterization of vapors of these molecules. In this article we present the C 1s, N 1s and Fe 2p photoemission results as well as N K-edge X-ray absorption data of iron phthalocyanine (FePc) in gas phase. Presented comparison of X-ray photoelectron spectroscopy and X-ray absorption spectroscopy spectra of FePc films show a great similarity with the gas phase results, confirming the molecular character of thick films. The Fe2p photoemission spectrum of the gas phase FePc, shown for the first time, can be considered as a fingerprint of the Fe(II) ionic state of the central metal of the iron phthalocyanine. The performed multiplet calculations for describing the Fe 2p XP spectrum indicate 3Eg (a1g2eg32g1) state as the most probable ground state for thick film of iron phthalocyanine.
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| 5. |
- Bidermane, Ieva, et al.
(författare)
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Experimental and theoretical study of electronic structure of lutetium bi-phthalocyanine
- 2013
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Ingår i: Journal of Chemical Physics. - : American Institute of Physics (AIP). - 0021-9606 .- 1089-7690. ; 138:23, s. 234701-
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Tidskriftsartikel (refereegranskat)abstract
- Using Near Edge X-Ray Absorption Fine Structure (NEXAFS) Spectroscopy, the thickness dependent formation of Lutetium Phthalocyanine (LuPc2) films on a stepped passivated Si(100)2x1 reconstructed surface was studied. Density functional theory (DFT) calculations were employed to gain detailed insights into the electronic structure. Photoelectron spectroscopy measurements have not revealed any noticeable interaction of LuPc2 with the H-passivated Si surface. The presented study can be considered to give a comprehensive description of the LuPc2 molecular electronic structure. The DFT calculations reveal the interaction of the two molecular rings with each other and with the metallic center forming new kinds of orbitals in between the phthalocyanine rings, which allows to better understand the experimentally obtained NEXAFS results.
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| 6. |
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| 7. |
- Bidermane, Ieva, 1984-
(författare)
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Structure and Electronic Properties of Phthalocyanine Films on Metal and Semiconductor Substrates
- 2014
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The current thesis presents fundamental studies of phthalocyanines (Pcs), a group of organic macro-cycle molecules. The use of phthalocyanine molecular films in devices with a variety of possible technological applications has been the reason of the many studies dedicated to such molecules during the last decades.Core and valence photoelectron spectroscopies (PES), X-ray absorption spectroscopy (XAS) and scanning tunneling microscopy (STM) techniques are used to study phthalocyanine molecules in gas phase and adsorbed on gold (111) and silicon Si(100)-2x1 substrates. Density functional theory (DFT) is used to obtain further insights in the electronic structure of the phthalocyanines.The aim of our studies is to get a deeper understanding into the molecule-molecule and molecule-substrate interactions, a fundamental requirement for improving the devices based on such molecular materials.Gas phase PES and XAS studies and single molecule DFT calculations are performed on the valence band (VB) of iron phthalocyanine (FePc), manganese phthalocyanine (MnPc) and metal-free phthalocyanine (H2Pc). The VB simulations have shown how the metal atom of the Pc influences the inner valence states of the molecules. The HOMO of the H2Pc and FePc is formed by mostly C2p states, whereas the HOMO of MnPc has mainly Mn3d character.PES studies of H2Pc on Au(111) have revealed the influence of the surface on the adsorption of the monolayer. XAS studies indicate formation of ordered monolayer with the Pc ligands parallel to the surface and the change of the molecular tilt angle with increasing thicknesses. For LuPc2 adsorbed on Au(111), STM study demonstrates a formation of bilayer instead of a monolayer.A comparison between the results of LuPc2 adsorbed on pristine or passivated Si(100)-2x1 confirmes the different reactivities of these surfaces: LuPc2 retains many molecular-like characters, when adsorbed on the innert passivated Si. Instead, on the more reactive pristine Si surface, the spectroscopic results have indicated a more significant interaction, possible hybridization and charge redistribution between the molecules and the surface. Moreover, STM images show a modification of the geometrical shape of the molecules, which are proposed to adsorb in two different geometries on the pristine Si surface.
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| 8. |
- Bidermane, Ieva, et al.
(författare)
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When the Grafting of Double Decker Phthalocyanines on Si(100)-2 × 1 Partly Affects the Molecular Electronic Structure
- 2016
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 120:26, s. 14270-14276
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Tidskriftsartikel (refereegranskat)abstract
- A combined X-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy (STM), and density functional theory (DFT) study has been performed to characterize the adsorbate interaction of lutetium biphthalocyanine (LuPc2) molecules on the Si(100)-2 × 1 surface. Large molecule–substrate adsorption energies are computed and are found to compete with the molecule–molecule interactions of the double decker molecules. A particularly good matching between STM images and computed ones confirms the deformation of the molecule upon the absorption process. The comparison between DFT calculations and XP spectra reveals that the electronic distribution in the two plateaus of the biphthalocyanine are not affected in the same manner upon the adsorption onto the silicon surface. This finding can be of particular importance in the implementation of organic molecules in hybrid devices.
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| 9. |
- Born, Artur, et al.
(författare)
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Quantification of Ni L-2,L-3 core-hole relaxation pathways utilizing Auger photoelectron coincidence spectroscopy
- 2021
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Ingår i: Physical Review B. - : American Physical Society. - 2469-9950 .- 2469-9969. ; 103:11
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Tidskriftsartikel (refereegranskat)abstract
- Ni LVV Auger spectra, in coincidence with the corresponding 2p(1/2), 2p(3/2), and 6 eV satellite photoelectrons, have been used to examine electron correlation and itinerance effects in Ni. In coincidence with the 2p(3/2) core level, the Auger spectral shape is represented by localized 3d(8) and itinerant valence final states with an additional 3d(7) Auger shake-up contribution. The spectra in coincidence with the 6 eV satellite probe the decay of localized 2p(5)3d(9) double hole states, leading to 3d(7) final states. It is found that a fraction of the double hole states delocalize before the Auger decay. A similar delocalization is observed for the double hole states produced by the L2L3M45 Coster-Kronig process, and the delocalization rates have been determined.
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| 10. |
- Boudet, S., et al.
(författare)
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Growth mode and self-organization of LuPc2 on Si(001)-2 x 1 vicinal surfaces : An optical investigation
- 2012
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Ingår i: Physical Review B. Condensed Matter and Materials Physics. - 1098-0121 .- 1550-235X. ; 86:11, s. 115413-
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Tidskriftsartikel (refereegranskat)abstract
- We report an investigation of the initial growth and of the self-organization of lutetium biphthalocyanine LuPc2 on Si(001)-2 x 1 vicinal surfaces. Using surface-sensitive optical spectroscopies, namely, surface-difference-reflectance spectroscopy (SDRS) and reflectance-anisotropy spectroscopy (RAS), together with local-probe microscopies, we are able to propose a scenario for the growth mode up to about 20 nm. We demonstrate that the growth mode initially proceeds through the formation of a wetting layer, followed by the formation of clusters whose sizes increase while keeping a constant shape in which the molecules are inclined. Moreover, the LuPc2 molecules are self-organized along the step edges, and we are able to estimate that about 30% to 100% of the molecules are aligned when considering that the molecules are tilted by 45 degrees to 63 degrees with respect to the surface normal.
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