Melanin films on Au(1 1 1): Adsorption and molecular conductance

We have studied the adsorption and electronic properties of thin melanin films on Au(1 1 1) by scanning tunneling microscopy (STM), scanning tunneling spectroscopy (STS), and density functional (DF) calculations. We have found that the minimum melanin unit detected under different adsorption conditions is consistent with the structural model for eumelanin protomolecules based on tetramer macrocycles formed by four monomer units (hydroquinone, indolequinone and its tautomers) with an inner porphyrin ring. DF calculations reveal that the entire π structure of the tetramers is implied in the chemisorption process through its frontier orbitals (HOMO and LUMO), a fact that is reflected in the change of intramolecular bonds. Also van der Waals interactions give an important contribution to the adsorption energy (≈0.02 eV/Å2). Dried thin melanin films (1 monolayer in thickness) exhibit good electronic conductance due to the presence of localized states near the Fermi level while dried thicker films exhibit a semiconductor-like behavior. Illumination of the thicker films with white light results in significant photo-induced tunneling currents when the melanin-covered Au is made negative with respect to the tip.

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► Ultrathin melanin films are deposited on Au(1 1 1) surface from aqueous solutions.
► One monolayer thick films are formed by oligomers consistent with tetramer models.
► Thick films exhibit metallic conduction while thicker has semiconductor behavior.
► DFT calculation with van der Waals of melanin tetramer adsorbed on Au(1 1 1) is done.
► Semiconductor film is photoactive when is irradiated with white light.