| AVS 66th International Symposium & Exhibition | |
| Thin Films Division | Wednesday Sessions |
| Session TF1-WeM |
| Session: | Vapor Deposition of Functional Polymer Thin Films and Composites |
| Presenter: | Kamal Baba, Luxembourg Institute of Science and Technology, Luxembourg |
| Authors: | K. Baba, Luxembourg Institute of Science and Technology, Luxembourg G. Bangasi, Luxembourg Institute of Science and Technology, Luxembourg G. Frache, Luxembourg Institute of Science and Technology, Luxembourg D. El Assad, Luxembourg Institute of Science and Technology, Luxembourg J. Desport, Luxembourg Institute of Science and Technology, Luxembourg K. Heinze, Johannes Gutenberg University of Mainz, Germany N.D. Boscher, Luxembourg Institute of Science and Technology, Luxembourg |
| Correspondent: | Click to Email |
Thanks to their remarkable functional properties, porphyrinic compound led to the development of various technological applications, including photovoltaic1 catalysis2 and sensing.3 Among this porphyrinic compounds, conjugated and directly fused porphyrins attracted strong attention.4 Indeed, the high conjugation of these systems provides additional interesting functional properties such as two photon absorption, near infrared absorption and enhanced electro-catalytic activity.5,6 However, while the solution-phase synthesis of directly fused porphyrin coatings has been successfully developed in recent years, the deposition of these promising compounds in thin film form has remained a challenge.
In this work, we report the simultaneous synthesis and deposition of conductive directly fused poly(porphyrin) coatings based on a substrate independent and up-scalable oxidative chemical vapor deposition (oCVD) approach. The direct fusion of nickel(II) 5,15-(diphenyl)porphyrin (NiDPP) is successfully achieved using different oxidants, such as iron(III) chloride (FeCl3), copper(II) chloride (CuCl2) and copper(II) perchlorate hexahydrate (Cu(ClO4)2·6H2O). The decisive reactions and side reactions during the oCVD process are evidenced by Lased Desorption Ionization High Resolution Mass Spectroscopy (LDI-HRMS) and UV-Vis-NIR absorption. FeCl3 is demonstrated to be the most suitable oxidant, allowing the formation of singly-fused poly(NiDPP) or conductive doubly or triply-fused poly(NiDPP) that strongly absorb in the near-infrared spectral region. Owing to the highly conjugated structure of the fused tapes, the deposited coatings films exhibit electrical conductivity up to 7×10−1 S cm−1 and strong absorption in the visible to near-infrared spectral region.
The described approach is not specific to NiDPP, providing the fact that meso-position remains available, other porphyrins can be fused and deposited in thin film form. Interestingly, the developed approach is inherently scalable and readily allows the deposition and patterning of conductive fused porphyrin thin films on sensitive substrates, such as printer paper or polymer foils, paving the way to the integration of directly fused porphyrin into advanced optoelectronic devices.
References:
1. S. Mathew, A. Yella, P. Gao et al., Nat. Chem. 2014, 6(3), 242–7
2. W. Zhang, W. Lai, R. Cao, Chem. Rev. 2017, 117(4), 3717–3797
3. Y. Ding, WH. Zhu, Y. Xie, Chem. Rev. 2017, 117(4), 2203–2256
4. T. Tanaka, A. Osuka, Chem. Soc. Rev. 2015, 44, 943–969
5. H. Mori, T. Tanaka, A. Osuka, J. Mater. Chem. C. 2013, 1, 2500–2519
6. D. Khusnutdinova, B.L. Wadsworth, M. Flores et al., ACS Catal. 2018, 8, 9888–9898