In this paper we focus on the structural, electronic, and magnetic properties of Ni tetra-phenyl-porphyrins (NiTPP) grown on top of Fe(001)–p(1 × 1)O. Ordered thin films of metal TPP molecules are potentially interesting for organic electronic and spintronic applications, especially when they are coupled to a ferromagnetic substrate. Unfortunately, porphyrin layers deposited on top of ferromagnetic substrates do not generally show long-range order. In this work, we provide evidence of an ordered disposition of the organic film above the iron surface and we prove that the thin layer of iron oxide decouples the molecules from the substrate, thus preserving the molecular electronic features, especially the HOMO-LUMO gap, even when just a few organic layers are deposited. The effect of the exposure to molecular oxygen is also investigated and an increased robustness against oxidation with respect to the bare substrate is detected. Finally, we present our results for the magnetic analysis performed by spin resolved spectroscopy, finding a null magnetic coupling between the molecules and the substrate.

Porous crystalline Ni-doped TiO₂ films were produced using DC plasma electrolytic oxidation in refrigerated H₂SO₄ aqueous solutions containing NiSO₄. The crystalline phase structure consisted of a mixture of anatase and rutile, ranging from ~30 to ~80 wt % rutile. The oxide films obtained at low NiSO₄ concentration showed the highest photocurrent values under monochromatic irradiation in the UV-vis range, outperforming pure TiO₂. By increasing NiSO₄ concentration above a threshold value, the photoelectrochemical activity of the films decreased below that of undoped TiO₂. Similar results were obtained using cyclic voltammetry upon polychromatic UV-vis irradiation. Glow discharge optical emission spectrometry (GD-OES) analysis evidenced a sulfur signal peaking at the TiO₂/Ti interface. XPS spectra revealed that oxidized Ni²⁺, S⁴⁺ and S⁶⁺ ions were included in the oxide films. In agreement with photocurrent measurements, photoluminescence (PL) spectra confirmed that less intense PL emission, i.e., a lower electron-hole recombination rate, was observed for Ni-doped samples, though overdoping was detrimental.

We give evidence of the formation of an ordered array of tetra-phenyl porphyrins (TPP) when these molecules are deposited on top of oxygen-passivated Fe(001), namely the Fe(001)-p(1 × 1)O surface. We also prove that they are magnetically coupled with the substrate. The ordered molecular packing, together with the magnetic coupling, are fundamental conditions for application in organic spintronic devices. The system is studied by means of spin-resolved photoemission spectroscopies and scanning tunneling microscopy.