The Application Of Acylhydrazone Porhyrin Metal Coordination Compounds As Hole Transport Material In Perovskite Solar Cells

Porphyrins and their derivatives with stronger intermolecularπ-πstacking have excellently photophysical and photochemical properties,which have been extensively studied in dye-sensitized solar cells（DSSCs）.Inspried by the excellent properities porphyrins and their derivatives,here,an acylhydrazone-based porphyrin derivative（ZnPy,ZnP,CuP）was used as HTM to prepare PSC.Acylhydrazone unit can achieve the efficiently electronic passivation of under-coordinated Pb atoms within the perovskite and improve the stability of perovskite.The spectral properties and thermal stability of hydrazone-based porphyrins were characterized.To proof the efficiently electronic passivation of under-coordinated Pb atoms in perovskite,the FTIR spectrum of the films with different components and modifications were carried out.Finally,the performance of the assembled devices coorperation with acyhydrazine-based porphyrins was tested based on mesoscopic configuration.The results are show as fellow:the absorption peak at 418 cm^-1 that was assigned to Pb-N vibration.These results clearly suggested the formation of Pb-N coordination-bond between porhyrin and perovskite,further the efficient electronic passivation of under-coordinated Pb atoms in perovskite.The results of electrochemical impedance spectroscopy（EIS）measurements indicated the presence of a decreased transfer resistance(R_tr)and an increased interfacial recombination resistance(R_rec)for the device with acylhydrazone-based porphyrin compared to the device with Spiro-OMeTAD,proof the efficient passivation of under-coordinated Pb atoms.In addition,the acylhydrazone units can accomplish an excellent charge transport,and porphyrin-basedcores with stronger intermolecularπ-πstacking have a higher hole mobility in their pristine form.Finally,the best efficiency of fabricated MAPbI₃（MA=CH₃NH₃⁺）PSCs was up to 18.2%for benefit from the redox shuttle of copper（I/II）for efficient charge transport.Notably,under same measurment condition,the devices cooperated with acylhydrazone-based porphyrin showed much better stability than Spiro-OMeTAD,especially for the thermal stability.Such a work provides another strategy for design new class HTMs based on porphyrin and their derivatives in efficient and stable PSCs.