A Surface Chemical Reaction in Organic–Inorganic Materials Using a New Chemical Evaporation System

Abstract

We report the surface reaction that occurs in organic-inorganic thin films using a hybrid deposition system that combines thermal evaporation (TE) and metalation process. Growth of a smooth, uniform organic-inorganic hybrid thin film was demonstrated, and the occurrence of a self-limited surface reaction between the organic semiconductor and the inorganic metal atom during metalation process was confirmed with X-ray photoelectron spectroscopy (XPS) and Raman analysis. In this study, we utilized a hybrid deposition system that combined TE and vapor phase-metalation to create an organic-inorganic hybrid thin film. Experimental data and theoretical simulation of a model system are also provided to explain the barrierless reaction that occurs during synthesis of a zinc tetraphenyl porphyrin (ZnTPP) thin film. This process can be utilized to increase the flexibility for the advanced synthesis of organic-inorganic hybrid thin films.

Water Formation for the Metalation of Porphyrin Molecules on Oxidized Cu(111)

“…We can discriminate three vacuum metalation methods for growing a porphyrin monolayer on surfaces, namely metal physical vapor deposition, substrate self‐metalation, and alternative routes based on the copresence of thermally unstable metal–organic molecules . Among the three methods, which of course have advantages and disadvantages, self‐metalation allows the use of only the free‐base porphyrins without any other reactant.…”

Selective coordination with heterogeneous metal atoms for inorganic–organic hybrid layers

“…2c-e), p-(H 6 )THPP, p-(H 2 )THPP-Sn(II), and Zn(II)-p-THPP-Sn(II) lms have growth rates of 0.352 nm s À1 , 0.434 nm s À1 , and 0.812 nm s À1 , respectively. When compared with the synthesis of ZnTPP in our previous work, 24 the metal-free p-(H 6 )THPP layer has a similar growth rate to that of ZnTPP lms, in which Zn atoms of the DEZ molecules were substituted into the center of p-(H 2 )THPP. However, in this study, Sn atoms were decorated only on the peripheral groups of p-(H 6 )THPP during the Sn metalation process of p-(H 2 )THPP-Sn(II).…”

Vapor-Phase Infiltration inside a Microporous Porphyrinic Metal–Organic Framework for Postsynthesis Modification

“…VPI of MIL-173(Zr) proceeds extremely quickly and efficiently compared to classical solution-based reactions and to VPI of porphyrinic monolayers, where pulses of several seconds were applied. 20 To check the effect of a longer TMA exposure time, the process was performed only with a single precursor pulse of 120 s, followed by a 15 min purge (note that 120 s is equivalent in time to 400 cycles of 0.3 s pules). Here again the reaction temperature did not have a meaningful effect because, at 50 and 170 °C, the Al/Zr ratios in the resulting material were of 0.85 and 0.8, respectively.…”

“…Such an infiltration of metal precursors and further metalation was not observed upon exposure to trimethylaluminum (TMA) and titanium isopropoxide during Al 2 O 3 or TiO 2 coatings, suggesting that the size of the precursor molecules played a critical role. Vapor-phase growth of a metalloporphyrin multilayer was demonstrated by Kim et al using a sequential approach . By alternatively evaporating free-base porphyrin on a surface and then exposing it to DEZ vapor that reacted with pyrrolic nitrogen in self-limiting manner, a 100-nm-thick hybrid thin film was achieved.…”

“…Vapor-phase growth of a metalloporphyrin multilayer was demonstrated by Kim et al using a sequential approach. 20 By alternatively evaporating free-base porphyrin on a surface and then exposing it to DEZ vapor that reacted with pyrrolic nitrogen in selflimiting manner, a 100-nm-thick hybrid thin film was achieved. Site-selective ALD took advantage of porphyrins covalently linked to a surface as nucleation sites to allow metallocluster growth as spatially separated islands.…”