Formation of an interphase layer during deposition of cobalt onto tetraphenylporphyrin: a hard X-ray photoelectron spectroscopy (HAXPES) studyElectronic supplementary information (ESI) available. See DOI: 10.1039/c6cp05894a

The interface formation upon vapor deposition of a metal onto a molecular organic semiconductor was studied using a well-defined complexation reaction between a metal and a porphyrin. Specifically, metallic cobalt (Co) was vapor deposited onto a thin film of 2 H -tetraphenylporphyrin (2HTPP) at room temperature. The resulting interface was probed with Hard X-ray Photoelectron Spectroscopy (HAXPES) using photon energies between 2 and 6 keV to obtain a detailed depth profile of the chemical composition. Characteristic changes in the N 1s core level signals reveal the formation of a cobalt tetraphenylporphyrin (CoTPP) layer between the Co and 2HTPP layers. Assuming an abrupt interface between CoTPP and 2HTPP (layer-by-layer model), analysis of the XPS data results in a thickness of the CoTPP reaction layer of 1.6 nm. However, a more advanced numerical analysis allowed us to reconstruct details of the actual depth distribution of the CoTPP interphase layer: up to a depth of 1.5 nm, all 2HTPP molecules were converted into CoTPP. Beyond this depth, the CoTPP concentration decreases sharply within 0.15 nm to zero. Chemical depth profiling of a metal/porphyrin interface with Hard X-ray Photoelectron Spectroscopy (HAXPES) reveals the formation of a 1.6 nm thick interphase layer.