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Conductive Fused Porphyrin Tapes on Sensitive Substrates by a Chemical Vapor Deposition Approach
摘要： Oxidative polymerization of nickel(II) 5,15-diphenyl porphyrin and nickel(II) 5,15-bis(di-3,5-tert-butylphenyl) porphyrin by an oxidative chemical vapor deposition (oCVD) approach yields multiply fused porphyrin oligomers in thin film form. The oCVD technique enables the formation, deposition and p-doping of conjugated poly(porphyrins) coatings in a single step without the use of solvents or post-treatments. The decisive reactions and side reactions during the oCVD process are evidenced by high-resolution mass spectrometry. Due to the highly conjugated structure of the fused porphyrin 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) thin films, even on sensitive substrates, is demonstrated by their successful deposition and patterning on glass, silicon and printer paper. The ability to form conductive poly(porphyrins) thin films could enable the design of a new category of optoelectronic devices using the oCVD approach.
关键词： Chemical Vapor Deposition,Polymerization,Oxidative Coupling,Porphyrins,Thin Films
更新于2025-09-23 15:22:29
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Conjugated HCl-doped polyaniline for photocatalytic oxidative coupling of amines under visible light
摘要： HCl-Doped polyaniline (PANI-ES) and PANIs of different oxidation states were prepared by a typical oxidative polymerization and subsequent redox reaction, respectively. The photocatalytic performance of PANIs towards selective benzylamine oxidation reactions under visible light was investigated. PANI-ES containing a polaron structure exhibited the highest light-induced activity (54.9%). The results show that the formation of the surface complex between PANI-ES and adsorbed amine should be responsible for the enhanced visible light activity. The newly formed polaron band in PANI-ES has a greater number of delocalized electrons, which can facilitate electron transfer and thus improve the photoactivity. These results indicate that conjugated conducting polymers can be efficient visible light-responsive nonmetal photocatalysts for green synthesis.
关键词： Conjugated polyaniline,Amines,Visible light,Oxidative coupling,Photocatalysis
更新于2025-09-19 17:15:36
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Forming a metal-free oxidatively-coupled agent, bicarbazole, as a defect passivation for HTM and an interfacial layer in a p-i-n perovskite solar cell exhibits nearly 20% efficiency
摘要： In this study we synthesized three simple and inexpensive (34–120 USD/g) 3,3′-bicarbazole–based hole transporting materials (BC-HTMs; NP-BC, NBP-BC and PNP-BC) through a metal-free oxidative coupling, in excellent yields (≥ 95%). These bicarbazoles contain phenylene or biphenylene substituents on the carbazole N atom, with extended π-conjugation achieved through phenylene units at the 6,6′-positions of the bicarbazole. When using NBP-BC as a dopant-free HTM in a p–i–n perovskite solar cell (PSC), we achieved a power conversion efficiency (PCE) of 13.04% under AM 1.5G conditions (100 mW cm–2); this PCE was comparable with that obtained when using PEDOT:PSS as the HTM (12.67%). BC-HTMs showed the large grain size (μm) of perovskite than PEDOT:PSS-based, due to defect passiviation on indium tin oxide (ITO) substrate and good hydrophobicity. Furthermore, we realized highly efficient and stable PSCs when using the p–i–n device structure ITO/NiOx/NP-BC/perovskite/PC61BM/BCP/Ag. The bifacial defect passivation effect of the interfacial layer improved the grain size of the perovskite layer and also enhanced the performance; the best performance of the NiOx/NP-BC device was characterized by a short-circuit current density (Jsc) of 22.38 mA cm–2, an open-circuit voltage (Voc) of 1.09 V, and a fill factor (FF) of 79.9%, corresponding to an overall PCE of almost 20%. This device structure has competitive potential because its performance is comparable with that of the record high efficiency PSCs. Under an Ar atmosphere, the PCE of the NiOx/NP-BC PSC device decayed by only 4.55% after 168 h; it retained 90.80% of its original PCE after 1000 h. A morphological study revealed that the films of the BC-HTMs were indeed smooth and hydrophobic, and that the perovskite films spin-coated upon them were uniform and featured large grains (micrometer scale). Time-resolved photoluminescence (TRPL) spectra of the perovskite films suggested that the hole extraction capabilities of the NiOx/BC-HTMs were better than that of the bare NiOx. The superior film morphologies of the NiOx/BC-HTMs were responsible for the performances of their devices being comparable with those of bare NiOx-based PSCs.
关键词： power conversion efficiency,3,3′-bicarbazole,perovskite solar cells,hole transporting materials,metal-free oxidative coupling,dopant-free
更新于2025-09-16 10:30:52
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Conductive Fused Porphyrin Tapes on Sensitive Substrates by a Chemical Vapor Deposition Approach
摘要： Oxidative polymerization of nickel(II) 5,15-diphenyl porphyrin and nickel(II) 5,15-bis(di-3,5-tert-butylphenyl) porphyrin by an oxidative chemical vapor deposition (oCVD) approach yields multiply fused porphyrin oligomers in thin film form. The oCVD technique enables the formation, deposition and p-doping of conjugated poly(porphyrins) coatings in a single step without the use of solvents or post-treatments. The decisive reactions and side reactions during the oCVD process are evidenced by high-resolution mass spectrometry. Due to the highly conjugated structure of the fused porphyrin 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) thin films, even on sensitive substrates, is demonstrated by their successful deposition and patterning on glass, silicon and printer paper. The ability to form conductive poly(porphyrins) thin films could enable the design of a new category of optoelectronic devices using the oCVD approach.
关键词： Porphyrins,Oxidative Coupling,Chemical Vapor Deposition,Thin Films,Polymerization
更新于2025-09-04 15:30:14