Conductive Fused Porphyrin Tapes on Sensitive Substrates by a Chemical Vapor Deposition Approach

Directly fused metalloporphyrin tapes were simultaneously synthesized and deposited in a thin film form by scalable and substrate‐independent chemical vapor deposition (CVD). Patterned and conductive (3.6×10⁻² S cm⁻¹) conjugated poly(porphyrin) thin films are formed. Mass spectrometry provides insight into the oxidative polymerization reaction and two side reactions (metalloporphyrin chlorination and π extension via intramolecular ring fusion).

Abstract

Oxidative polymerization of nickel(II) 5,15‐diphenyl porphyrin and nickel(II) 5,15‐bis(di‐3,5‐tert‐butylphenyl) porphyrin by oxidative chemical vapor deposition (oCVD) yields multiply fused porphyrin oligomers in thin film form. The oCVD technique enables one‐step formation, deposition, and p‐doping of conjugated poly(porphyrins) coatings without solvents or post‐treatments. The decisive reactions and side reactions during the oCVD process are shown by high‐resolution mass spectrometry. Owing to the highly conjugated structure of the fused tapes, the thin films exhibit an electrical conductivity of 3.6×10⁻² S cm⁻¹ and strong absorption in the visible to near‐infrared spectral region. The formation of smooth conjugated poly(porphyrins) coatings, even on sensitive substrates, is demonstrated by deposition and patterning on glass, silicon, and paper. Formation of conductive poly(porphyrins) thin films could enable the design of new optoelectronic devices using the oCVD approach.

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