THESE Présentée en vue de l’obtention du grade de DOCTEUR DE L’UNIVERSITE PARIS-SEINE Spécialité: Chimie Organique – Science des matériaux Soutenue publiquement 16 May 2019 par: Diego A. MAGALDI-LARA Synthesis of New Carbazole-based Hole Transport Molecules for Hybrid Perovskite Solar Cells Devant le jury composé de : Pr. Thierry TOUPANCE Université de Bordeaux Examinateur Pr. Hyacinthe RANDRIAMAHAZAKA Université Paris Diderot Rapporteur Dr. Kathleen MOINEAU-CHANE CHING CNRS Toulouse Rapporteur Dr. Frédéric DUMUR Aix-Marseille Université Examinateur Pr. Fabrice GOUBARD Université de Cergy-Pontoise Directeur de thèse Dr. Thanh-Tuân BUI Université de Cergy-Pontoise Co-encadrant ECOLE DOCTORALE SCIENCES ET INGENIERIE (Université de Cergy-Pontoise) Unité de recherche: LPPI, Laboratoire de Physicochimie des Polymères et des Interfaces, EA2528 2 Glossary ACN acetonitrile AFM atomic force microscopy bl blocking layer CE counter electrode CTA chain transfer agent CV cyclic voltammetry Cz carbazole D/A donor/acceptor DCM dichloromethane DFT density functional theory DMF dimethylformamide DPA 4,4′-dimethoxydiphenylamine DSC differential scanning calorimetry DSSC dye sensitized solar cell DVB divinylbenzene Egap energy bandgap Eox oxidation onset ETL electron transport layer FF fill factor FTO fluor-tin oxide glass HR-MS high-resolution mass spectroscopy HTL hole transport layer HTM hole transport material ITO indium-tin oxide glass JSC short-circuit current MAI methylammonium iodide MAPI methylammonium lead triiodide (MAPbI3) MeOH methanol 3 MO molecular orbital NMR nuclear magnetic resonance OSC organic solar cell PCBM phenyl-C61-butyric acid methyl ester PCE power conversion efficiency PDOT-PSS poly(3,4-ethylenedioxythiophene) polystyrene sulfonate PET polyethylene terephthalate Peth Petroleum ether PSC perovskite solar cell PV photovoltaic Ra arithmetic mean roughness Rq root mean square roughness sDSSC solid-dye sensitized solar cell SEC size-exclusion chromatography TGA thermogravimetric analysis TPA 4-bromo-N,N-bis(4-methoxyphenyl)aniline VOC open-circuit voltage WE working electrode η photocurrent conversion efficiency SN2 nucleophilic substitution 4 Contents Glossary .................................................................................................................................................. 3 Contents.................................................................................................................................................. 5 Introduction ............................................................................................................................................ 9 1. State of the art: from the solar energy to the photovoltaic devices .................................................... 15 1.1 Photovoltaic Overview ........................................................................................................... 16 The aim of this thesis ..................................................................................................................... 17 1.2 State of the Art: emergent hybrid photovoltaics .......................................................................... 18 1.2.1 Dye-sensitized solar cells ....................................................................................................... 18 1.2.2 Perovskite solar cell............................................................................................................... 20 1.3 Device Architecture and Perovskite Solar Cells (PSCs) .................................................................. 26 1.3.1 Perovskite Configuration ....................................................................................................... 26 1.3.2 Mesoporous electron transport layer .................................................................................... 26 1.3.3 Mesoporous insulating PSC ................................................................................................... 28 1.3.4 Planar PSC ............................................................................................................................. 29 1.3.5 HTM-free PSC ........................................................................................................................ 30 1.3.6 Inverted PSC .......................................................................................................................... 31 1.4 Device Components: Semiconductor TiO2 layer as dense ETL layer ............................................... 33 1.5 Device Components: Mesoporous ETL layer and interface with Perovskite material ..................... 34 1.6 Device Components: Perovskite as active layer ............................................................................ 36 1.7 Device Components: Hole transport material ............................................................................... 38 1.7.1 Inorganic p-type HTM............................................................................................................ 39 1.7.2 Organic small molecules as Hole Transport Materials ............................................................ 40 1.8 Contact metallic layer .................................................................................................................. 42 1.9 Carbazole as organic hole transport materials .............................................................................. 43 2. Carbazole substituted Isomers derivatives as HTM for perovskite solar cells ...................................... 51 5 2.1 Strategy ....................................................................................................................................... 52 2.2 Synthesis objective ...................................................................................................................... 53 2.3 Synthesis of DMx and iDMX molecules ......................................................................................... 54 Synthetic strategy of DMx or 3,6-carbazole substituted molecules ................................................. 54 Synthetic strategy of iDMx or 2,7-carbazole substituted molecules ................................................ 54 2.3.1 Synthetic procedures ............................................................................................................ 55 2.3.1.3 General synthesis procedure for compounds DM1 and DM2. ............................................. 57 2.4 Characterization of physical properties of these carbazole species ............................................... 64 2.4.1 Thermal properties ............................................................................................................... 64 2.4.2 Optical properties ................................................................................................................. 72 2.4.3 Electrochemistry measurements ........................................................................................... 75 2.4.4 General physical properties table of DMx and i-DMx series ................................................... 79 2.4.5 Computational Studies .......................................................................................................... 81 2.4.6 Surface morphology studies by atomic force microscopy ...................................................... 83 2.5 Photovoltaic measurements ........................................................................................................ 88 2.5.1 Characterization of solar cells ................................................................................................ 90 2.5.2 Analysis and discussion ......................................................................................................... 90 2.5.3 Photovoltaic performance of iDMx ........................................................................................ 92 2.5.4 Contact angle over MAPbI3 surface ....................................................................................... 93 2.5.5 Light soaking effect ............................................................................................................... 96 2.6 Conclusions .................................................................................................................................. 99 3. Carbazole-based polymeric/oligomeric hole transporting materials ................................................. 101 3.1 State of the art ........................................................................................................................... 102 3.2 Carbazole non-conjugated polymer DM1P ................................................................................. 106 3.2.1 Material synthesis ............................................................................................................... 106 3.2.3 Characterization of DM1P ................................................................................................... 112 3.2.4 General physical properties of DM1P .................................................................................. 119 6 3.2.5 Photovoltaic Performances ................................................................................................. 120 3.2.6 Conclusions ......................................................................................................................... 122 3.3 Carbazole based conjugated Oligomer ......................................................................................