Electronic structure at transition metal phthalocyanine-transition metal oxide interfaces: Cobalt phthalocyanine on epitaxial MnO films.

The electronic structure of the interface between cobalt phthalocyanine (CoPc) and epitaxially grown manganese oxide (MnO) thin films is studied by means of photoemission (PES) and X-ray absorption spectroscopy (XAS). Our results reveal a flat-lying adsorption geometry of the molecules on the oxide surface which allows a maximal interaction between the π-system and the substrate. A charge transfer from MnO, in particular, to the central metal atom of CoPc is observed by both PES and XAS. The change of the shape of N-K XAS spectra at the interface points, however, to the involvement of the Pc macrocycle in the charge transfer process. As a consequence of the charge transfer, energetic shifts of MnO related core levels were observed, which are discussed in terms of a Fermi level shift in the semiconducting MnO films due to interface charge redistribution.

Communication: Influence of graphene interlayers on the interaction between cobalt phthalocyanine and Ni(111).

The influence of graphene interlayers on electronic interface properties of cobalt phthalocyanine on Ni(111) is studied using both photoemission and X-ray absorption spectroscopy. A charge transfer associated with a redistribution of the d-electrons at the Co-atom of the phthalocyanine occurs at the interface to Ni(111). Even a graphene buffer layer cannot prevent the charge transfer at the interface to Ni(111); however, the detailed electronic situation is different.

Adsorption and bonding of first layer and bilayer terephthalic acid on the Cu(100) surface by high-resolution electron energy loss spectroscopy.

The self-assembled and highly ordered first layer of terephthalic acid on Cu(100) as well as its bilayer on the same surface are studied here using high-resolution electron energy loss spectroscopy (HREELS), Auger electron spectroscopy, and low energy electron diffraction. These experiments show completion of the first layer before growth of the second layer. HREELS measurements show that the first layer of the acid deprotonates, which is seen in the absence of the OH stretching mode for the acid groups. However, this mode is present in the bilayer structure, confirming that the deprotonation is due to a reaction with the Cu surface and suggesting that there is little mixing of the layers. It has been suggested previously that the TPA monolayer structure is stabilized by an intermolecular hydrogen bonding interaction, but we are not able to resolve any distortion of the CH stretching mode for such an interaction, but instead see evidence for direct bonding to the Cu surface.

Enhancement of Radiative Plasmon Decay by Hot Electron Tunneling.

Here we demonstrate that photon emission induced by inelastic tunneling through a nanometer single gap between a sharp Au tip and an Au substrate can be significantly enhanced by the illumination of the junction with 634 nm laser light with an electric field component oriented parallel to the tip-axis, i.e., perpendicular to the sample. Analyzing photoluminescence (PL) spectra recorded as a function of bias voltage allows us to distinguish between PL from (1) the decay of electron-hole pairs created by the laser excited sp/d interband transition with a characteristic band at 690 nm and (2) the red-shifted radiative decay of characteristic plasmon modes formed by the gap. Since the electroluminescence spectra (without laser) already show the plasmonic gap modes, we conclude that the enhanced intensity induced by laser illumination originates from the radiative decay of hot electrons closely above the Fermi level via inelastic tunneling and photon emission into the plasmon modes. Since these processes can be independently controlled by laser illumination and the amplitude of the bias voltage, it is of great interest for designing new switchable photon emission plasmonic devices.

Superluminescence from an optically pumped molecular tunneling junction by injection of plasmon induced hot electrons.

Here, we demonstrate a bias-driven superluminescent point light-source based on an optically pumped molecular junction (gold substrate/self-assembled molecular monolayer/gold tip) of a scanning tunneling microscope, operating at ambient conditions and providing almost three orders of magnitude higher electron-to-photon conversion efficiency than electroluminescence induced by inelastic tunneling without optical pumping. A positive, steadily increasing bias voltage induces a step-like rise of the Stokes shifted optical signal emitted from the junction. This emission is strongly attenuated by reversing the applied bias voltage. At high bias voltage, the emission intensity depends non-linearly on the optical pump power. The enhanced emission can be modelled by rate equations taking into account hole injection from the tip (anode) into the highest occupied orbital of the closest substrate-bound molecule (lower level) and radiative recombination with an electron from above the Fermi level (upper level), hence feeding photons back by stimulated emission resonant with the gap mode. The system reflects many essential features of a superluminescent light emitting diode.