A quantum chemistry study on the performance of porphyrin-based solar cell sensitisers; Zinc and anchor group position effects

Abstract

In this work, ten porphyrin derivatives, including free-base zinc-metalised compounds were studied by varying the position of the carboxyl anchoring group and the alkyl substituents length on the remaining three phenyl rings with the aim of the cell efficiency investigation. Theoretical performances of the sensitisers in the dye-sensitised solar cell systems have been discussed by analysis of the optical absorption, the oxidised potential of ground and excited states, light-harvesting efficiency and electron injection efficiency. Due to lower symmetry of free-based porphyrins, they showed broader bands than zinc porphyrins. The second group sensitisers are better than the first one due to the smaller oxidation potential energy, higher open-circuit voltage and light-harvesting efficiency. The influence of long alkyl substituents on the photovoltaic parameters is not perceptible but ortho and meta positions of anchoring group modify the solar cell performance. Finally, some correlations between the quantum reactivity indices and photovoltaic parameters have obtained and discussed.

Photoexcitation Processes in Oligomethine Cyanine Dyes for Dye-Sensitized Solar Cells—Synthesis and Computational Study

“…To avoid that a mistake is perpetuated, it should be noted that in the literature there are several reports using a wrong relation to determine V oc (see, for instance, References. [65][66][67][68][69][70][71][72][73][74]). In those cases, a confusion is made with the driving force for charge injection from the dye into the semiconductor, ∆G inj , which is calculated as the difference between the energy of the excited state of the dye (lowest unoccupied molecular orbital in DFT calculations), E dye* , and the TiO 2 conduction band edge, E CB [10,63,75]:…”

Anchoring Group and π-Spacer Effects on the Dynamics and Kinetics of the Photovoltaic Processes in the Quinoxaline-Based Organic Dye-Sensitized Solar Cells

“…39 These parameters are molecular descriptors, which are important for investigation of the chemical stabilities and charge transfer in the solar cells. 40,41 All calculations were performed by Gaussian 09 computational package. 42 The performance of the solar cells is determined by the IPCE influenced by the possibility of electron transfer between the energy levels of the dye and TiO 2 /dye conditions.…”

“…DFT reactivity indices such as the electronic chemical hardness, η, electronic chemical potential, μ, and the electrophilicity index, ω, were calculated according to the Koopman’s theorem . These parameters are molecular descriptors, which are important for investigation of the chemical stabilities and charge transfer in the solar cells. , All calculations were performed by Gaussian 09 computational package…”

Structure and photophysical and electrochemical properties of a copper porphyrin complex with a three-dimensional framework

“…As far as is known, porphyrins are famous for their vital roles in the red blood cells of animals and the green leaves of plants; as a result, porphyrins have become one of the most widely investigated chemical systems and have drawn much attention as wonderful functional materials. Due to their comparability to the natural photosynthetic chlorophyll pigment, easy preparation, intensive optical absorptions and emissions, long lifetimes of the singlet and triplet states, and favourable redox potential (Kadish et al, 2000;Chambron et al, 2000;Gust & Moore, 2000), porphyrins offer a very versatile synthetic base for many kinds of materials which have different applications in many disciplines of physics and chemistry, such as solar cells and opto-electronics (Khan & Sayyad, 2012;Seol et al, 2012;Arkan et al, 2015;Xia et al, 2015;Ørnsø et al, 2015), catalysis (Chen et al, 2019;Zhang et al, 2018;Mokary Yazdely et al, 2019), sensors (Ma et al, 2019;Wu et al, 2018;Zhao et al, 2019) and molecular sieves (Anjali et al, 2018;Hou et al, 2014).…”