Heterometallic Porphyrin Conjugated Polymer Thin Films—A Gas‐Phase Approach for the Engineering of New Fused Porphyrin Systems

Abstract For the first time, the simultaneous synthesis and deposition of heterometallic porphyrin conjugated polymer thin films from a simple and scalable gas‐phase approach are reported. The oxidative chemical vapor deposition (oCVD) reaction of 5,15‐(diaryl) porphyrins chelated with different metal cations (M = Co(II), Ni(II), Zn(II), Cu(II), Pd(II)) readily yields the formation of new hetero‐metalated fused porphyrin tapes, such as evidenced by in‐depth high‐resolution mass spectrometry studies. The impact of the coreactants on the regioselectivity of the intermolecular dehydrogenative coupling reaction and the formation of double or triple bonds between the porphyrin units is demonstrated. The oCVD reaction of multiple porphyrins brings the possibility to easily engineer the chemical features and the electronic and optoelectronic properties of these highly conjugated porphyrin polymers. Particularly, it is demonstrated that porphyrin conjugated polymers having different chelated metal cations can achieve higher electrical conductivities and promote narrower bandgaps. The gas‐phase approach presented herein overcomes the main limitations of the conventional solution‐based approaches and opens the path to the engineering of a novel class donor–acceptor heterometallic polymers with high interest in several fields including multimetallic electrocatalysis, photocatalysis, sensing, and nonlinear optics applications

Molecular Engineering of Porphyrin‐Tapes/Phthalocyanine Heterojunctions for a Highly Sensitive Ammonia Sensor

International audienceModulating the interfacial charge alignments by molecular engineering in an organic heterojunction device is a smart strategy to improve its conductivity, which can be exploited in high performance gas sensors development. Herein, the fabrication of new organic heterojunction devices based on porphyrin tapes and phthalocyanines and their potentiality in ammonia sensing at different relative humidity (rh) are investigated. The devices are built using dry approach relying on oxidative chemical vapor deposition for simultaneous synthesis, doping and deposition of the porphyrin tape layer and physical vapor deposition of phthalocyanine layer. The association of the porphyrin tapes with copper phthalocyanine (CuPc) or its perfluorinated analogue (Cu(F16Pc)) in a bilayer device configuration revealed a non-linear current-voltage characteristics, assigned to the formation of organic heterojunction at the bilayer interface. Cu(F16Pc)-based devices revealed higher response, faster sorption kinetics, stable baseline and less interference from rh fluctuations towards ammonia than CuPcbased devices which are attributed to more conducting interface in the former. Moreover, depending on the porphyrin tape associated, Cu(F16Pc)-based devices exhibited sensitivit

Highly Efficient 2D Materials Engineered Perovskite/Si Tandem Bifacial Cells Beyond 29%

International audiencePerovskite/Silicon tandem technology represents a promising route to achieve 30% power conversion efficiency (PCE), by ensuring low levelized costs energy. In this article, we develop a mechanically stacked 2T perovskite/silicon tandem solar cell, with subcells independently fabricated, optimized, and subsequently coupled by contacting the back electrode of the mesoscopic perovskite top cell with the texturized and metalized front contact of the silicon bottom cell. The possibility to separately optimize the two sub-cells allows to carefully choose the most promising device structure for both top and bottom cells. Indeed, semitransparent perovskite top cell performance is boosted through the use of selected two-dimensional materials to tune the device interfaces. In addition, a protective buffer layer is used to prevent damages induced by the transparent electrode sputtering deposition over the hole transporting layer. A textured amorphous/crystalline silicon heterojunction cell fabricated with a fully industrial in-line production process is here used as state of art bottom cell. The perovskite/c-Si tandem device demonstrates remarkable PCE of 28.7%. Moreover, we demonstrate the use of a bifacial silicon bottom cell, as a viable way for overcoming the current matching constrain imposed by the 2T configuration. Here, the current generation difference between perovskite and c-Si cells is compensated by exploiting the albedo radiation thanks to the bifaciality of the commercial c-Si cell used in this article. Considering standard rear irradiation, final power generation density above 32 mW/cm 2 can be achieved, paving the way for a tandem technology customable according to the final installation site