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Highly photoactive chemically modified thin films of chloroaluminum (and bromoaluminum) phthalocyanines probed by NEXAFS and UPS: Determination of the electronic structure and the molecular orientation

Journal Article · · Journal of Physical Chemistry; (USA)
DOI:https://doi.org/10.1021/j100154a049· OSTI ID:5878460
;  [1]; ;  [2]; ;  [3];  [4]
  1. Universite Paris-Sud, Orsay (France)
  2. INRS-Energie, Varennes, Quebec (Canada)
  3. Univ. of Arizona, Tucson (USA)
  4. Brookhaven National Lab., Upton, NY (USA)
Near edge x-ray absorption fine structure (NEXAFS) at the C and N K edges and UV photoelectron spectroscopy (UPS) at variable excitation energy (21.2 and 120 eV) have been used to characterize the electronic structure and the molecular orientation of chloroaluminum phthalocyanine (ClAlPc) thin films deposited on glass or SnO{sub 2} substrates and subjected to chemical transformations. Transformation H occurs when the films are soaked in an aqueous acidic solution, while transformation I is observed if I{sub 3}{sup {minus}}/I{sup {minus}} is added to the solution. It is demonstrated that the protonation of the aza nitrogen atoms of ClAlPc happens during both transformations. It modifies the valence band of the compound but has no effect on the unoccupied levels of the material. Besides the protonation, the uptake of I{sub 3}{sup {minus}} in the phthalocyanine film during transformation I leads to the formation of a charge-transfer complex between the phthalocyanine and the iodine species with a modification of both the occupied and unoccupied levels of the material. The band gap is reduced by 0.3 eV and 1.5 eV for transformations H and I, respectively. No orientation-dependent effect is observed when the chloroaluminum phthalocyanine is deposited on SnO{sub 2}. On the contrary, strong polarization effects are observed in the NEXAFS spectra of phthalocyanine deposited on a float glass substrate.
OSTI ID:
5878460
Journal Information:
Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 95:1; ISSN 0022-3654; ISSN JPCHA
Country of Publication:
United States
Language:
English