研究目的
To achieve the one-step synthesis, deposition, and doping of multiply fused porphyrin oligomers using an oxidative chemical vapor deposition (oCVD) approach for potential applications in optoelectronic devices.
研究成果
The oCVD approach successfully enables the one-step synthesis, deposition, and doping of multiply fused porphyrin oligomers into conductive thin films with an electrical conductivity of 3.6×10–2 S·cm–1 for NiDPP. The technique is versatile, allowing deposition on sensitive substrates like paper, and patterning for optoelectronic applications. Side reactions, while initially seen as limitations, may be leveraged to enhance material stability and conjugation. Future work should focus on optimizing the process and exploring applications in devices such as solar cells and sensors.
研究不足
The insolubility of the oCVD NiDPP coating prevents detailed mass distribution analysis via GPC. The limited range of LDI-HRMS (up to 4000 m/z) restricts observation of longer oligomers. Side reactions such as chlorination and intramolecular cyclization occur, which may affect material properties. The conductivity of oCVD NiDDt-BuPP coating is significantly lower due to reduced polymerization length and dopant concentration.
1：Experimental Design and Method Selection:
The study employs an oxidative chemical vapor deposition (oCVD) approach to synthesize and deposit fused porphyrin thin films. The oCVD process involves vapor phase delivery of a monomer (nickel(II) porphyrins) and an oxidant (iron(III) chloride) to a substrate under reduced pressure (10–3 mbar). The reaction is performed in a customized stainless steel chamber with heated crucibles for sublimation.
2：Sample Selection and Data Sources:
The monomers used are nickel(II) 5,15-diphenyl porphyrin (NiDPP) and nickel(II) 5,15-bis(di-3,5-tert-butylphenyl) porphyrin (NiDDt-BuPP), selected for their hydrolytic stability and availability of unsubstituted positions. Substrates include printer paper, glass slides, silicon wafers, and organic field-effect transistor (OFET) chips.
3：List of Experimental Equipment and Materials:
Equipment includes a customized oCVD reactor with heated crucibles and stage, high-resolution mass spectrometer (LDI-HRMS), UV-Vis-NIR spectrometer, gel permeation chromatography (GPC), scanning electron microscope (SEM), atomic force microscope (AFM), and X-ray photoelectron spectrometer (XPS). Materials include NiDPP, NiDDt-BuPP, FeCl3 oxidant, and various solvents for solubility tests.
4：Experimental Procedures and Operational Workflow:
The oCVD reaction is conducted at 10–3 mbar pressure. NiDPP is sublimed at 250°C, FeCl3 at 170°C, and substrates are placed on a heated stage 20 cm above. Coatings are formed and characterized using UV-Vis-NIR spectroscopy, LDI-HRMS, GPC, SEM, AFM, XPS, and conductivity measurements. Patterning is done using masks.
5：Data Analysis Methods:
Data analysis involves interpreting UV-Vis-NIR spectra for absorption characteristics, LDI-HRMS for oligomer identification, GPC for molecular weight distribution, SEM and AFM for morphology, XPS for elemental composition, and conductivity measurements using Ohm's law.
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