Dissertations / Theses on the topic 'Perovskite Solar Cells Hybrid perovskites'

[ES] El objetivo principal de esta tesis es contribuir al avance de nuevas técnicas de elaboración con bajo coste, utilizando materiales tipo de cobre, indio, galio y selenio CIGS y Perovskita para aplicaciones en energía solar fotovoltaica. CIGS parecen ser adecuadas ya que son de bajo costo de producción y se han reportado eficiencias de conversión del 23,35%. Por otro lado, las perovskitas híbridas de haluros de plomo orgánicos-inorgánicos han aparecido como nuevos materiales excepcionales para celdas solares, especialmente porque la eficiencia de las celdas solares basadas en perovskita ha aumentado del 3.8% al 22.7% en menos de un lustro. Este trabajo se ha dedicado a experimentar sobre la elaboración y caracterización de CIGS y los perovskitas de metilamonio de yoduro de plomo de (MAPbI3) y formamidinio de yoduro de plomo (FAPbI3), que se utilizo tanto en la aplicación a las células solares de perovskitas y en las células Tándem CIGS-perovskita. Las películas se caracterizaron por difracción de rayos X, espectroscopía Raman, microscopía electrónica de barrido, análisis de espectroscopía de energía dispersiva, microscopía de fuerza atómica, transmisión electrónica microscopía, fotoluminiscencia y espectroscopia UV-Vis. En las capas de CIGS depositadas por electrodeposición se investigó el efecto de diferentes parámetros, También investigamos en detalle el efecto del contacto posterior en las propiedades estructurales y ópticas de CIGS. Constatamos que el tipo de contacto posterior tiene un efecto significativo en el rendimiento posterior de las películas delgadas CIGS. Además, estudiamos la técnica de espray pirólisis para producir películas CIGS. Se estudió el proceso de recocido, que es el factor clave para mejorar el rendimiento de las células solares. Se elaboraron diferentes películas delgadas constituidas de nuestro dispositivo CdZnS/CdS/CIGS/Mo eso utilizó una capa conductora transparente de CdZnS para minimizar la alineación de la interfaz. Por otro lado, se analizó el proceso de cristalización y la estabilidad de las capas MAPbI3. Las capas de MAPbI3 se trataron añadiendo antisolvente a diferentes velocidades. Durante el tratamiento se producen intercambios complejos que influencian muchas propiedades fisicoquímicas. Se investigaron las propiedades ópticas y eléctricas de las películas de MAPbI3. Para mejorar la estabilidad de MAPbI3, se incorporó tetrabutilamonio (TBA), observando una mejora en la formación de la estructura perovskita que crece en la dirección preferente (110). La fase cristalina de MAPbI3 dopada con TBA presenta mejor cristalinidad, gran tamaño de grano, morfología superficial sin poros lo que es adecuado para la fabricación de dispositivos optoelectrónicas con mayor rendimiento. Además, hemos identificado el impacto de TBA en las propiedades foto físicas de MAPbI3. En las muestras de TBA:MAPbI3 aumenta la intensidad de la fotoluminiscencia al reducir la densidad de los estados de trampa y la absorción óptica muestra un cambio significativo hacia longitudes de onda más largas y la banda prohibida óptica varió de 1.8 a 1.52 eV. Finalmente, las muestras dopadas con 5% TBA mejoraron su estabilidad y se encontró que después de 15 días la estabilidad permanecía excelente en una humedad de ~ 60%. Por otra parte, investigamos el efecto de guanidinio (GA) sobre las propiedades estructurales y ópticas de FAPbI3. La relación entre la fase a de perovskita deseable y la fase indeseable y se ha estudiado en función del contenido de GA. Se comprobó que el dopaje con GA es eficaz en el control de la relación de fases a/y y luego en la estabilización de la fase a. Los resultados muestran que añadiendo una cantidad adecuada del 10% GA conduce a una mejora de película de perovskita que se evidencia en la homogeneidad de la fase a estable, granos de mayor tamaño y capas libres de poros. Además, 10% GA:FaPbI3 demostraron una excelente estabilidad después de ser envejecidas durante 15 días en un ambiente con humedad relativa del 60%.
[EN] The thesis work presented is part of the work in the Laboratory of New Materials for Photovoltaic Energy in the main target to use low cost techniques for elaboration of Perovskite and Copper, indium, gallium, and selenium CIGS materials for photovoltaic application. Organic-inorganic lead halides perovskites have currently and exceptionally appeared as new materials for low cost thin film solar cells specially that the efficiency of perovskite based solar cell have jumped from 3.8% to 22.7% in short time.in other hand, CIGS solar cells record 23.35% efficiency and still can be boosted. Here, we report the elaboration and characterization of CIGS as well as methylammonium lead iodide perovskites MAPbI3 and formamidinuim iodide lead iodide perovskites FAPbI3 absorbers for perovskite-based solar cells and Tandem Perovskites/ CIGS. The thin films prepared were characterized by X-ray diffraction (XRD), Raman spectroscopy (RS), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) analysis, atomic force microscopy (AFM), transmission electron microscopy (TEM), Photoluminescence analysis (PL) and UV-Vis spectroscopy. The first stage was devoted for the effect of different parameters on the growth of CIGS by electrodeposition and we investigate the impact of different back contact in structural and optical proprieties. In a second stage, we report the growth of CIGS films by spray pyrolysis, we studied the effect of experimental parameter also the annealing process which is the key factor for improving the performance of solar cells,subsequently we elaborated different films constituted CdZnS/CdS/CIGS/Mo solar cells, the approach is to change the toxic ZnO by using a transparent, conductive CdZnS layer. In other hand, MAPbI3 film was investigated in order to optimize the chemical composition and to study the crystallization process also to get sight about the stability of perovskite materials to meet the requirement of their application as an active layer in perovskite solar cell. For this purpose. the MAPbI3 film surface was treated by adding diethyl ether antisolvent with different rates. during the treatment complex exchanges are appearing at the same time under the influence of quite a lot of physicochemical properties. A whole understanding of this topic is critically important for improving solar cell performance. MAPbI3 doped by the tetrabutylammonium TBA is boosting the formation of perovskite structure, leading to a higher orientation along the (110) and shows better crystallinity, large grain size, pinhole-free, which is suitable for the manufacturing of the optoelectronic devices with higher performance. Also, we have identified the impact of TBA in the photo-physical properties, we have noticed that the TBA improve the photoluminescence emission by reducing the density of trap states and the optical absorption indicates a significant shift to the lower wavelength and optical bandgap varied from 1.8 to 1.52 eV. Finally, the stability was explored for 5% TBA, it found that after 15 days the stability remained excellent in relative humidity of ~60%. These results would be helpful for realizing stable and high performance MAPbI3-based devices. Furthermore, we inspect the effect of monovalent cation substitution of Guanidinium (GA) on the structural and optical properties of FAPbI3 thin films perovskites. The ratio between the desirable a-phase and the undesirable y yellow phase is studied as a function of GA content. GA doping is shown to be efficient in the control of a/y phases ratio and then in the stabilization of the a-FaPbI3 phase. We qualitatively evaluate the impact of 10% of guanidinium on the phase composition and microstructure of films. The results show that an adequate amount of 10% GA:FaPbI3 leads to a homogeneous perovskite film with stable a phase, large grains, and free pinholes. 10% GA: FaPbI3 films demonstrate excellent stability after aging for 15 days in relative humidity of~60%.
[CA] L'objectiu principal d'aquesta tesi és contribuir a l'avanç de noves tècniques d'elaboració de baix cost, fent servir materials d'aliatges del tipus de coure, indi, gal·li i seleni (CIGS) i perovskites, per a aplicacions en energia solar fotovoltaica. El CIGS sembla ser adequat ja que són de baix cost de producció i s'han reportat eficiències de conversió del 23,35%. D'altra banda, les perovskites híbrides d'halurs de plom orgànics-inorgànics han aparegut com a nous materials excepcionals per cel·les solars, especialment perquè l'eficiència de les cel·les solars basades en perovskites ha augmentat del 3.8% al 22.7% en menys d'un lustre. En el present treball, reportem l'elaboració i caracterització de CIGS y de perovskitas de iodur de plom de metilamoni (MAPbI3) i de iodur de plom de formamidini (FaPbI3) per a les cèl·lules solars de CIGS i tàndem Perovskites/CIGS. En les capes de CIGS dipositades per electrodeposició es va investigar l'efecte dels diferents paràmetres sobre el procés d'electrodeposició, així com l'efecte del contacte posterior sobre les propietats estructurals i òptiques del CIGS. Ens trobem que el tipus de contacte posterior té un efecte significatiu en la posterior interpretació de pel·lícules primes CIGS. A més, vam estudiar la tècnica de polvorització de la piròlisi per produir pel·lícules de CIGS. Es va estudiar el procés de recuit, que és el factor clau per millorar el rendiment de les cèl·lules solars. Es van produir diferents pel·lícules fines formades pel nostre dispositiu CdZnS/CdS/CIGS/Mo que utilitzaven una capa conductiva CdZnS transparent per minimitzar l'alineació de la interfície. D'altra banda, es van investigar perovskites MAPbI3, amb la finalitat d'optimitzar la composició química i estudiar el procés de cristal·lització també per a conèixer l'estabilitat dels materials de perovskita. la cristal·lització s'aconsegueix alentint la solubilitat en una solució saturada mitjançant l'addició d'una quantitat diferent de l'antisolvent d'èter dietílic. Durant el tractament apareixen al mateix temps intercanvis complexos sota la influència de moltes propietats fisicoquímiques. Una comprensió completa d'aquest tema és de vital importància per a millorar el rendiment. Amb l'objectiu principal d'augmentar l'estabilitat de MAPbI3, el tetrabutilamoni (TBA) es pot incorporar a MAPbI3, impulsant la formació de l'estructura de perovskita, la qual cosa porta a una major orientació al llarg de (110). MAPbI3 dopades amb TBA presenten una millora de la cristalinitat, major grandària, la qual cosa és adequada per a la fabricació de dispositius optoelectròniques de major rendiment. A més, hem identificat l'impacte de TBA en les propietats foto físiques de MAPbI3. Hem notat que el dopatge amb TBA millora tant l'emissió de la fotoluminiscència en reduir la densitat dels estats de trampes com l'absorció òptica on apareix un canvi significatiu de la banda òptica prohibida cap a longituds d'ona més llargues que significa disminuir l'energia del gap, que va variar de 1.8 a 1.52 eV. Finalment, es va explorar l'estabilitat per les perovsquites dopades amb 5%TBA. Es va trobar que després de 15 dies l'estabilitat romania excel·lent en un humitat de 60%. A més, hem estudiat FAPbI3 com un dels materials de perovskita més atractius. Hem investigat l'efecte de la substitució de guanidini (GA) sobre les propietats estructurals i òptiques de FAPbI3. La relació entre la fase a de perovskita desitjable i la fase indesitjable y es va estudiar en funció del contingut de GA. Es mostra que el dopatge amb GA és eficaç en el control de la relació de fases a /y i després en l'estabilització de la fase a-FaPbI3. Els resultats mostren que una quantitat adequada de 10% GA condueix a una pel·lícula homogènia amb fase a estable, grans grans lliures de porus i forats. Les pel·lícules de 10% GA:FaPbI3 demostraren una excel·lent estabilitat després de l'envelliment durant 15 dies en un ambient humit (humitat relativa de 60%).
Bouich, A. (2020). Study and Characterization of Hybrid Perovskites and Copper-Indium-Gallium Selenide thin films for Tandem Solar Cells [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/160621
TESIS

Metal-halide perovskites show great promise as solution-processable semiconductors for efficient solar cells and LEDs. In particular, the diffusion range of photogenerated carriers is unexpectedly long and the luminescence yield is remarkably high. While much effort has been made to improve device performance, the barriers to improving charge transport and recombination properties remain unidentified. I first explore charge transport by investigating a back-contact architecture for measurement. In collaboration with the Snaith group at Oxford, we develop a new architecture to isolate charge carriers. We prepare thin films of perovskite semiconductors over laterally-separated electron- and hole-selective materials of SnOₓ and NiOₓ, respectively. Upon illumination, electrons (holes) generated over SnOₓ (NiOₓ) rapidly transfer to the buried collection electrode, leaving holes (electrons) to diffuse laterally as majority carriers in the perovskite layer. We characterise charge transport parameters of electrons and holes, separately, and demonstrate that grain boundaries do not prevent charge transport. Our results show that the low mobilities found in applied-field techniques do not reflect charge diffusivity in perovskite solar cells at operating conditions. We then use the back-contact architecture to investigate recombination under large excess of one charge carrier type. Recombination velocities under these conditions are found to be below 2 cm s⁻¹, approaching values of high quality silicon and an order of magnitude lower than under common bipolar conditions. Similarly, diffusion lengths of electrons and holes exceed 12 μm, an order of magnitude higher than reported in perovskite devices to date. We report back-contact solar cells with short-circuit currents as high as 18.4 mA cm⁻², giving 70% external charge-collection efficiency. We then explore the behaviour of charge carriers in continuously illuminated metal-halide perovskite devices. We show that continuous illumination of perovskite devices gives rise to a segregated charge carrier population, and we find that the distance photo-induced charges travel increases significantly under these conditions. Finally, we examine intermittancy in the photoluminescence intensity of metal-halide perovskite films.

Depuis 5 ans, les pérovskites hybrides organiques-inorganiques sont apparues comme une nouvelle classe de semiconducteurs possédant des propriétés optoélectroniques très intéressantes pour les dispositifs photovoltaïques et émetteurs de lumière. Cette thèse porte sur une étude expérimentale de spectroscopie optique, qui s’inscrit dans le champ d’exploration des propriétés optiques et des effets excitoniques des pérovskites hybrides CH3NH3PbX3 avec X = I ou Br. Nous avons étudié les propriétés optiques de couches minces déposées par spin-coating et de monocristaux élaborés en solution. Les couches minces présentent une structure granulaire et une densité élevée de défauts qui induisent une grande variabilité des propriétés optiques. L’étude des monocristaux nous a permis de mettre en évidence les propriétés intrinsèques du matériau : émission d’excitons libres, couplage électron-phonon, dynamique de recombinaison des porteurs de charge. De plus, nous avons exploré l’impact de la transition de phase orthorhombique-tétragonale sur les propriétés optiques de CH3NH3PbI3. Enfin, nous avons quantifié l’effet de la réabsorption sur les propriétés d’émission des pérovskites hybrides. L’estimation précise de cet effet est particulièrement importante pour l’interprétation des propriétés optiques des pérovskites hybrides et explique la grande hétérogénéité des résultats dans la littérature
In the last five years, hybrid organic-inorganic perovskites have emerged as a novel class of semiconductors owing to their interesting electronic and optical properties for photovoltaic and light-emitting devices. This thesis reports an experimental study using optical spectroscopy to explore the optical properties and excitonic effects of hybrid perovskites such as CH3NH3PbX3 with X = I or Br.We studied the optical properties of spin-coated thin films and solution processed single crystals. Thin films present a granular structure and a high density of defects which induce a great variability of the optical properties. The study of single crystals allows us to highlight the intrinsic properties of material: free exciton emission, electron-phonon coupling and charge carriers recombination dynamics. Besides, we have investigated the impact of the orthorhombic-tetragonal phase transition on the optical properties of CH3NH3PbI3. Finally, we have quantified the effect of reabsorption on the emission properties of hybrid perovskites. The accurate estimate of this effect is particularly important for the interpretation of the optical properties of hybrid perovskites and explains the great heterogeneity of the results in the literature

Les pérovskites hybrides célèbrent cette année leurs 10e anniversaire dans le domaine du photovoltaïque. En plus de la progression inégalée des rendements des cellules solaires, les pérovskites ont des propriétés optoélectroniques ajustables et peuvent être fabriquées par des procédés bas coûts, ce qui en fait de sérieuses candidates pour les cellules solaires multijunctions. Le réseau cristallin caractéristique des pérovskites hybrides offre une certaine liberté, supportant l’introduction partielle de cations et d’ions halogénures multiples. L’ajustement de la composition d’un matériau pérovskite se traduit par un ajustement de ces propriétés électroniques dont notamment sa structure de bandes. En adaptant la composition il est possible d’obtenir un matériau pérovskite avec une bande interdite de 1,7 eV qui serait parfaitement adapté pour une cellule tandem à base de Silicium cristallin. Les films minces de pérovskites peuvent être fabriqués par une grande diversité de techniques de dépôt, à partir de précurseurs ‘bon marché’ (CH3NH3I et PbI2 par exemple), par des procédés à basse température. Même si la grande majorité des films de pérovskites sont obtenus par la méthode d’enduction centrifuge, celle-ci ne permet pas l’obtention de films homogènes, sur grandes surfaces et de façon répétable. Etant donné l’enjeu industriel qui attend les pérovskites et l’intérêt croissant pour les structures tandems Silicium/Pérovskite, les méthodes sans solvant semblent plus adaptées. Déjà très largement utilisé dans l’industrie des OLEDs, le procédé de coévaporation thermique semble constituer une solution commercialement viable. Publiée pour la première fois en 2013, la synthèse par coévaporation des pérovskites est pour le moment encore étudiée par peu de groupes, car nécessitant des équipements plus coûteux. La présente thèse vise à mettre en place et développer la technique de coévaporation pour la fabrication de films de pérovskites hybrides pour des applications en cellules solaires.Afin d’évaluer la faisabilité du procédé, nous avons commencé notre travail sur un réacteur de démonstration, ce qui nous a permis d’appréhender la réponse à la sublimation des deux précurseurs. Nous avons très vite identifié le comportement du sel organique CH3NH3I comme étant problématique car difficilement contrôlable (s’évaporant sous forme de « nuage »), comme nous l’avions lu dans la littérature. En six mois d’utilisation de ce réacteur, nous avons fabriqué des films de pérovskites ayant permis d’atteindre des rendements de 9% sur des cellules solaires, malheureusement avec une faible reproductibilité (que nous expliquons en partie par le caractère aléatoire de l’évaporation du composé organique CH3NH3I). Nous nous sommes trouvés dans l’incapacité de comprendre plus en profondeur le procédé à cause d’un manque de fonctionnalités de l’équipement. Grâce à ces différents retours d’expérience nous avons pu concevoir, en étroite collaboration avec l’équipementier, un réacteur semi-industriel dédié à la fabrication de films de perovskites par coévaporation. Suite à sa mise en place, nous nous somme focalisé sur la problématique de la reproductibilité dans nos expériences en essayant de diminuer l’impact du nuage organique. Bien que les efficacités atteintes en cellules solaires pour des films coévaporés fussent moindres que pour des films déposés par la technique classique d’enduction centrifuge, nous soupçonnions néanmoins une meilleure homogénéité des films obtenus par voie sèche. Nous avons ainsi intégré à cette thèse une étude comparative voie liquide/voie sèche par le biais d’une technique de spectromicroscopie rayons X en Synchrotron
Hybrid perovskites celebrate this year their 10-year anniversary in the photovoltaic field. Besides the unprecedented rise in solar cells efficiencies, perovskite materials have tunable optical properties and can be manufactured at low cost, making them very promising candidates for the high efficiency, multijunction solar cells strategy. Perovskite crystal structure offers a relative degree of freedom, allowing the partial integration of multiple cations and halide ions. This chemical composition tuning translates into a bandgap tuning. Through fine chemical engineering, the 1.7 eV requirement for a c-Si-based tandem device can be achieved. Perovskite thin films can be prepared by a large variety of deposition techniques, from low cost precursors (CH3NH3I and PbI2 for instance), through low-temperature processes. While most of the reported works on perovskite thin films are based on the basic wet-process spincoating technique, this latter hardly allows large scale, homogeneous and reproducible deposition. With the future challenge of industrialization and the increasing interest for the Silicon/Perovskite tandem approach, solvent-free methods appear more suitable. Already widely implemented in the OLED industry, coevaporation stands as a viable option for perovskites’ future. Reported for the first time in 2013, coevaporated perovskites are still scarcely studied compared to wet-based techniques, requiring more expensive set ups. In the present thesis, we implemented and developed the coevaporation process to fabricate perovskite thin films for solar cells applications.Starting off on a proof-of-concept reactor to assess the feasibility of the technique, we got accustomed to the perovskite precursors behaviour and identify very early on the organic precursor to be hardly manageable, as reported in the literature. In six months, we were nonetheless able to obtain nice perovskite films leading to 9% efficient photovoltaic devices, unfortunately with a poor reproducibility that we think to be partially due to the cloud vapour behaviour of CH3NH3I. We eventually found ourselves missing some features on the equipment, preventing us from accurately get a grasp on the process. From this feedback we then designed, hand in hand with the manufacturer, a dedicated semi-industrial equipment for perovskite coevaporation. Following its implementation, we then focused on establishing the reproducibility of the method, trying to mitigate the parasitic effect of the organic compound. Even though the efficiencies in solar cells were still slightly lower for coevaporated perovskites, with respect to classical spincoated ones, we expected the material homogeneity to be in favour of the vacuum-based process. We then eventually integrated to this thesis a comparative study between wet- and dry-processed perovskite films using a Synchrotron-based X-ray spectromicroscopy technique

Over the last five years hybrid organic-inorganic metal halide perovskites have attracted strong interest in the solar cell community as a result of their high power conversion efficiency and the solid opportunity to realise a low-cost as well as industry-scalable technology. Nevertheless, several aspects of this novel class of materials still need to be explored and the level of our understanding is rapidly and constantly evolving, from month to month. This dissertation reports investigations of perovskite solar cells with a particular focus on their local chemical composition. The analytical characterisation of such devices is very challenging due to the intrinsic instability of the organic component in the nanostructured compounds building up the cell. STEM-EDX (Scanning Transmission Electron Microscopy - Energy Dispersive X-ray spectroscopy) was employed to resolve at the nanoscale the morphology and the elemental composition of the devices. Firstly, a powerful procedure, involving FIB (Focus Ion Beam) sample preparation, the acquisition of STEM-EDX maps and the application of cutting edge post-processing data techniques based on multivariate analysis was developed and tested. The application of this method has drastically improved the quality of the signal that can be extracted from perovskite thin films before the onset of beam-induced transformations. Morphology, composition and interfaces in devices deposited by using different methodologies and external conditions were then explored in detail by combining multiple complementary advanced characterisation tools. The observed variations in the nanostructure of the cells were related to different photovoltaic performance, providing instructive indications for the synthesis and fabrication routes of the devices. Finally, the main degradation processes that affect perovskite solar cells were probed. STEM-EDX was used in conjunction with the application of in situ heating, leading to the direct observation of elemental species migration within the device, reported here for the first time with nanometric spatial resolution. Further analyses, involving a set of experiments aimed to study the effects of air exposure and light soaking on the cells, were designed and performed, providing evidence of the main pathways leading to the drastic drop in the device performance.

This thesis presents a study of hybrid solar cells, specifically looking at various methods which can be employed in order to increase the power conversion efficiency of these devices. The experiments and results contained herein also present a very accurate picture of how rapidly the field of hybrid solar cells has progressed within the past three years. Chapters 1 and 2 present the background and motivation for the investigations undertaken, as well as the relevant theory underpinning solar cell operation. Chapter 2 also gives a brief review of the literature pertinent to the main types of devices investigated in this thesis; dye-sensitised solar cells, semiconductor sensitized solar cells and perovskite solar cells. Descriptions of the synthetic procedures, as well as the details of device fabrication and any measurement techniques used are outlined in Chapter 3. The first set of experimental results is presented in Chapter 4. This chapter outlines the synthesis of mesoporous single crystals (MSCs) of anatase TiO₂ as well as an investigation of its electronic properties. Having shown that this material has superior electronic properties to the conventionally used nanoparticle films, they were then integrated into low temperature processed dye-sensitised solar cells and achieved power conversion efficiencies of > 3%, exhibiting electron transport rates which were orders of magnitude higher than those obtained for the high temperature processed control films. Chapter 5 further investigates the use of MSCs in photovoltaic devices, this time utilising a more strongly absorbing inorganic sensitiser, Sb₂S₃. Utilising the readily tunable pore size of MSCs, these Sb₂S₃ devices showed an increase in voltage and fill factor which can be attributed to a decrease in recombination within these devices. This chapter also presents the use of Sb₂S₃ in the meso-superstructured configuration. This device architecture showed consistently higher voltages suggesting that in this architecture, charge transport occurs through the absorber and not the mesoporous scaffold. Chapters 6 and 7 focus on the use of hybrid organic-inorganic perovskites in photovoltaic devices. In Chapter 6 the mixed halide, lead-based perovskite, CH₃NH₃PbI_3-xCl_x is employed in a planar heterojunction device architecture. The effects of Lewis base passivation on this material are investigated by determining the photoluminescence (PL) lifetimes and quantum efficiencies of treated and untreated films. It is found that passivating films of this material using Lewis bases causes an increase in the PLQE at low fluences as well as increasing the PL lifetime. By globally fitting these results to a model the trap densities are extracted and it is found that using these surface treatments decreases the trap density of the perovskite films. Finally, these treatments are used in complete solar cells resulting in increased power conversion efficiencies and an improvement in the stabilised power output of the devices. Chapter 7 describes the materials synthesis and characterisation of the tin-based perovskite CH₃NH₃SnI₃ and presents the first operational, lead-free perovskite solar cell. The work presented in this thesis describes significant advances in the field of hybrid solar cells, specifically with regards to improvements made to the nanostructured electrode, and the development and implementation of more highly absorbing sensitizers. The improvements discussed here will prove to be quite important in the drive towards exploiting solar power as a clean, affordable source of energy.

Philosophiae Doctor - PhD
The organic-inorganic hybrid perovskites such as methyl ammonium lead iodide (MAPbI3) or mixed halide MAPbI3-xClx (x is usually very small) have emerged as an interesting class of semiconductor materials for their application in photovoltaic (PV) and other semiconducting devices. A fast rise in PCE of this material observed in just under a decade from 3.8% in 2009 to over 25.2% recently is highly unique compared to other established PV technologies such as c-Si, GaAs, and CdTe. The high efficiency of perovskites solar cells has been attributed to its excellent optical and electronic properties. Perovskites thin film solar cells are usually deposited via spin coating, vacuum thermal evaporation, and chemical vapour deposition (CVD).

Les perovskites organiques-inorganiques en halogénures de plomb sont des matériaux très prometteurs pour la prochaine génération de cellules solaires avec des avantages intrinsèques tels que leur faible coût de fabrication (grande disponibilité des matériaux de base et leur mise en œuvre à basse température) et leur bon rendement de conversion photovoltaïque. Cependant, les cellules solaires pérovskites sont encore instables et montrent des effets d'hystérésis courant-tension délétères. Dans cette thèse, des résultats de l’analyse physique de couches minces de pérovskite à base de CH3NH3PbI3-xClx et de cellules solaires ont été présentés. Les caractéristiques de transport électrique et les processus de vieillissement ont été étudiés avec différentes approches.Dans une première étape, la synthèse du matériau pérovskite a été optimisée en contrôlant les conditions de dépôt des films en une seule étape telles que la vitesse de rotation (6000 rpm) de la tournette et la température de recuit des films (80 °C). Dans un second temps, des cellules solaires perovskites à base de CH3NH3PbI3-xClx ont été fabriquées en utilisant la structure planaire inversée et caractérisées optiquement et électriquement.Grace à l’utilisation de la spectroscopie optique à décharge luminescente (GDOES), un déplacement des ions halogénures a été observé expérimentalement et de façon directe sous l’application d’une tension électrique. Une longueur de diffusion ionique de 140 nm et un rapport de 65% d'ions mobiles ont été déduits. Il est montré que l'hystérésis courant-tension dans l'obscurité est fortement affectée par la migration des ions halogénures provoquant un écrantage substantiel du champ électrique appliqué. Nous avons donc trouvé sous obscurité un décalage de la tension à courant nul jusque 0,25 V et un courant de fuite jusque 0,1 mA / cm2 en fonction des conditions de mesure. Grâce aux courbes courant-tension en fonction de la température, nous avons déterminé la température de transition de la conductivité ions/électrons à 260K et analysé les résultats expérimentaux en utilisant l'équation de Nernst- Einstein donnant une énergie d'activation de 0.253 eV pour les ions mobiles.Enfin, le processus de vieillissement de la cellule solaire a été étudié avec des mesures optiques et électriques. Nous avons déduit que le processus de vieillissement apparaît d'abord à la surface des cristaux de pérovskite ainsi qu’aux joints de grains. Les mesures GDOES nous indiquent que les caractéristiques électriques des cellules pérovskites sont perdues par une corrosion progressive de l'électrode supérieure en argent causée par la diffusion des ions iodures
Organic-inorganic lead halide perovskites are very promising materials for the next generation of solar cells with intrinsic advantages such as a low-cost material due to the availability of source materials and low-temperature solution processing as well as a high power conversion efficiency of the sunlight. However, perovskite solar cells are still unstable and show deleterious current-voltage hysteresis effects. Inthis thesis, analyses of CH3NH3PbI3-xClx based perovskite thin films and solar cells are presented. The electrical transport characteristics and the ageing processes are investigated using different approaches.The synthesis of the halide perovskite materials is optimized in a first step by controlling the deposition conditions such as annealing temperature (80°C) and spinning rate (6000 rpm) in the one step-spin-casted process. CH3NH3PbI3-xClx based perovskite solar cells are then fabricated in the inverted planar structure and characterized optically and electrically in a second step.Direct experimental evidence of the motion of the halide ions under an applied voltage has been observed using glow discharge optical emission spectroscopy (GDOES). Ionic diffusion length of 140 nm and ratio of mobile iodide ions of 65 % have been deduced. It is shown that the current-voltage hysteresis in the dark is strongly affected by the halide migration which causes a substantial screening of the applied electric field. Thus we have found a shift of voltage at zero current (< 0.25 V) and a leakage current (< 0.1 mA/cm2) in the dark versus measurement condition. Through the current-voltage curves as a function of temperature we have identified the freezing temperature of the mobile iodides at 260K. Using the Nernst-Einstein equation we have deduced a value of 0.253 eV for the activation energy of the mobile ions.Finally, the ageing process of the solar cell has been investigated with optical and electrical measurements. We deduced that the ageing process appear at first at the perovskite grain surface and boundaries. The electrical characteristics are degraded through a deterioration of the silver top-electrode due to the diffusion of iodides toward the silver as shown by GDOES analysis

Solar energy as the most abundant source of energy is clean, non-pollutant, and completely renewable, which provides energy security, independence, and reliability. Organic-inorganic hybrid perovskite solar cells (PSCs) revolutionized the photovoltaics field not only by showing high efficiency of above 22% in just a few years but also by providing cheap and facile fabrication methods. In this dissertation, fabrication of PSCs in both ambient air conditions and environmentally controlled N2-filled glove-box are studied. Several characterization methods such as SEM, XRD, EDS, Profilometry, four-point probe measurement, EQE, and current-voltage measurements were employed to examine the quality of thin films and the performance of the PSCs. A few issues with the use of equipment for the fabrication of thin films are addressed, and the solutions are provided. It is suggested to fabricate PSCs in ambient air conditions entirely, to reduce the production cost. So, in this part, the preparation of the solutions, the fabrication of thin films, and the storage of materials were performed in ambient air conditions regardless of their humidity sensitivity. Thus, for the first part, the fabrication of PSCs in ambient air conditions with relative humidity above ~36% with and without moisture sensitive material, i.e., Li-TFSI are provided. Perovskite materials including MAPbI3 and mixed cation MAyFA(1-y)PbIxBr(1-x) compositions are investigated. Many solution-process parameters such as the spin-coating speed for deposition of the hole transporting layer (HTL), preparation of the HTL solution, impact of air and light on the HTL conductivity, and the effect of repetitive measurement of PSCs are investigated. The results show that the higher spin speed of PbI2 is critical for high-quality PbI2 film formation. The author also found that exposure of samples to air and light are both crucial for fabrication of solar cells with larger current density and better fill factor. The aging characteristics of the PSCs in air and vacuum environments are also investigated. Each performance parameter of air-stored samples shows a drastic change compared with that of the vacuum-stored samples, and both moisture and oxygen in air are found to influence the PSCs performances. These results are essential towards the fabrication of low-cost, high-efficiency PSCs in ambient air conditions. In the second part, the research is focused on the fabrication of high-efficiency PSCs using the glove-box. Both single-step and two-step spin-coating methods with perovskite precursors such as MAyFA(1-y)PbIxBr(1-x) and Cesium-doped mixed cation perovskite with a final formula of Cs0.07MA0.1581FA0.7719Pb1I2.49Br0.51 were considered. The effect of several materials and process parameters on the performance of PSCs are investigated. A new solution which consists of titanium dioxide (TiO2), hydrochloric acid (HCl), and anhydrous ethanol is introduced and optimized for fabrication of quick, pinhole-free, and efficient hole-blocking layer using the spin-coating method. Highly reproducible PSCs with an average power conversion efficiency (PCE) of 15.4% are fabricated using this solution by spin-coating method compared to the conventional solution utilizing both spin-coating with an average PCE of 10.6% and spray pyrolysis with an average PCE of 13.78%. Moreover, a thin layer of silver is introduced as an interlayer between the HTL and the back contact. Interestingly, it improved the current density and, finally the PCEs of devices by improving the adhesion of the back electrode onto the organic HTL and increasing the light reflection in the PSC. Finally, a highly reproducible fabrication procedure for cesium-doped PSCs using the anti-solvent method with an average PCE of 16.5%, and a maximum PCE of ~17.5% is provided.

Dès à présent, le monde est face à des enjeux majeurs : augmentation de la production d'énergie, réduction des impacts de la production et de la consommation d'énergie sur l'environnement. La transition vers des énergies durables a déjà commencé. Le photovoltaïque a sa place parmi les énergies renouvelables qui permettront de relever ce défi. Ce travail de thèse porte sur les pérovskites hybrides halogénées et plus particulièrement leur utilisation dans des cellules solaires. En effet très récemment, ces matériaux ont attiré l'attention de la communauté scientifique en raison de leurs propriétés optoélectroniques remarquables : bande interdite directe, forte absorption de la lumière, longueurs importantes de diffusion des porteurs, propriétés optoélectroniques accordables mais aussi une fabrication aisée et à bas coût. En quelques années, le rendement a connu une augmentation spectaculaire de 3,8 % en 2009 à 22,7 % en 2017. Ainsi, ces derniers résultats placent les cellules pérovskites comme des concurrents potentiels face aux cellules solaires à base de silicium cristallin qui représentent aujourd'hui 90 % des cellules en service. Dans la conception des cellules solaires à base de pérovskite, la couche de pérovskite est généralement intercalée entre deux couches de transporteurs de charges : les couches de transporteurs d'électron et de trou (ETM et HTM, respectivement). La qualité de ces couches est essentielle pour obtenir de hauts rendements. Dans ce travail, les propriétés optoélectroniques des pérovskites halogénées sont étudiées ainsi que plusieurs couches de transport de charge
In the future, the world has to face up to major challenges: increasing the energy production, reducing the environmental impact, moving towards sustainability in energy, etc. Renewable energies such as photovoltaics can meet these challenges. This thesis concerns hybrid halide perovskite materials and their use in solar cells. These materials have recently attracted a lot of attention owing to their direct bandgaps, strong light absorption, large carrier diffusion lengths, tunable optoelectronic properties, and their facile and low-cost fabrication In few years, their energy conversion efficiency has rapidly increased from 3.8 % in 2009 to 22.7 % in 2017, hence approaching efficiencies of crystalline silicon based-devices which represent 90% of commercial photovoltaic cells. In the design of perovskite cells, the perovskite photoabsorber is generally sandwiched by two interfacial layers that yield selective charge collections: the hole and electron transport layers (HTM and ETM). Good quality and adapted interfacial layers are required to obtained high efficiency cells. In this thesis, both the perovskite material and the interfacial layers are investigated

Perovskite solar cells have attracted much attention both in research and industrial domains. An unprecedented progress in development of hybrid perovskite solar cells (HPSCs) has been seen in past few years. The power conversion efficiencies of HPSCs has been improved from 3.8% to 24.2% in less than a decade, rivaling that of silicon solar cells which currently dominate the solar cell market. Hybrid perovskite materials have exceptional opto-electrical properties and can be processed using cost-effective solution-based methods. In contrast, fabrication of silicon solar cells requires high-vacuum, high-temperature, and energy intensive processes. The combination of excellent opto-electrical properties and cost-effective manufacturing makes hybrid perovskite a winning candidate for solar cells. As power conversion efficiencies of HPSCs improves beyond that of the established solar cell technology and their long-term stability increases, one of the crucial hurdles in the path to commercialization remaining to be adequately addressed is the cost-effective scalable fabrication. Spin-coating is the prevailing method for fabrication of HPSCs in laboratories. However, this technique is limited to small areas and results in excessive material waste. Two types of scalable manufacturing methods have been successfully demonstrated to fabricate HPSCs: (i) meniscus-assisted coating such as doctor-blade coating and slot-die coating; and (ii) dispersed deposition based on the coalescence of individual droplets, such as inkjet printing and spray coating. Electrospray printing belongs to the second category with advantages of high material utilization rate and patterning capability along with the scalability and roll-to-roll compatibility. In Chapter 3 of this dissertation, electrospray printing process is described for manufacturing of HPSCs in ambient conditions below 150 C. All three functional layers were printed using electrospray printing including perovskite layer, electron transport layer, and hole transport layer. Strategies for successful electrospray printing of HPSCs include formulation of the precursor inks with solvents of low vapor pressures, judicial choice of droplet flight time, and tailoring the wetting property of the substrate to suppress coffee ring effects. Implementation of these strategies leads to pin-hole free, low surface roughness, and uniform perovskite layer, hole transport layer and electron transport layer. The power conversion efficiency of the all electrospray printed device reached up to 15.0%, which is among the highest to date for fully printed HPSCs. The most efficient HPSCs rely on gold and organic hole-transport materials (HTMs) for achieving high performance. Gold is also chosen for its high stability. Unfortunately, the high price of gold and high-vacuum along with high-temperature processing requirements for gold film is not suitable for the large-scale fabrication of HPSCs. Carbon is a cheap alternative electrode material which is inert to hybrid perovskite layer. Due to the ambipolar transport property of hybrid perovskite, perovskite itself can act as a hole conductor, and the extra hole transport layer can be left out. Carbon films prepared by doctor-blade coating method have been reported as the top electrode in HPSCs. The efficiencies of these devices suffer from the poor interface between the doctor-blade coated carbon and the underlying perovskite layer. In Chapter 4, electrospray printing was applied for the fabrication of carbon films and by optimizing the working distance during electrospray printing, the interface between carbon and the underlying perovskite layer was greatly improved compared to the doctor-blade coated carbon film. The resulting HPSCs based on the electrospray printed carbon electrode achieved higher efficiency than that based on doctor-blade method and remarkably, this performance is close to that of gold based devices. In Chapter 5, preliminary results are provided on the laser annealing of hybrid perovskite films to further advance their scalable manufacturing. All layers of HPSCs require thermal annealing at temperature over 150 C for about half an hour or longer. The time-consuming conventional thermal annealing complicates the fabrication process and is not suitable for continuous production. High temperature over150 C is also not compatible with flexible substrates such as PET. Laser annealing is a promising method for overcoming these issues. It has several other advantages including compatibility with continuous roll-to-roll printing, minimal influence on non-radiated surrounding area, and rapid processing. Laser annealing can be integrated with the electrospray process to realize the continuous fabrication of hybrid perovskite film. Rapid laser annealing process with optimized power density and scanning pattern is demonstrated here for annealing perovskite films. The resulting hybrid perovskite film is highly-crystalline and pin-hole free, similar to that obtained from conventional thermal annealing.
Doctor of Philosophy

[ES] Las perovskitas orgánicas-inorgánicas de haluros de metilamonio y plomo y sus mezclas han mostrado propiedades optoelectrónicas óptimas como absorbente ideal para aplicaciones fotovoltaicas. Los dispositivos solares basados en perovskita han evolucionado rápidamente, desde una eficiencia del 3.9% en 2009, al 22.7% en 2017 y con un coste de fabricación más bajo que las células solares de silicio. Una desventaja del uso de absorbentes de perovskita en dispositivos fotovoltaicos es su baja estabilidad. Las células con un alto rendimiento, pierden su eficiencia y se degradan rápidamente. Para poder producir estos materiales industrialmente es necesario realizar estudios en profundidad que mejoren la eficiencia y estabilidad. Una vía de mejora es la ingeniería composicional, estrategia que hemos empleado en la elaboración de esta tesis y que consiste en la investigación y mejora de las propiedades optoelectrónicas y morfológicas, derivadas de la sustitución y/o combinación de cationes y aniones, que constituyen el material de perovskita. Se sintetizaron polvos puros de perovskita de I, Br, Cl, a partir de los cuales se prepararon capas puras y mixtas MAPbX3-xYx, con el objetivo de mejorar sus propiedades optoelectrónicas y estructurales. Los análisis de difracción de rayos X mostraron las propiedades estructurales de los polvos cristalinos y capas puras y mixtas. Los análisis de UV-vis y fotoluminiscencia mostraron que el rango de absorción varía a lo largo del espectro visible en función del contenido del haluro en las capas. Los análisis de fotoluminiscencia y calorimetría diferencial de barrido muestran los cambios de fase de las perovskitas puras a distintas temperaturas, coincidiendo dichos cambios en ambos análisis. El análisis FESEM de las perovskitas puras mostró las diferencias morfológicas entre los polvos y capas. Siguiendo esta línea de investigación, se estudiaron con más detalle las perovskitas mixtas de yodo-bromo, con un contenido de bromo de hasta el 33%, consiguiendo ajustar el bandgap para evitar pérdidas en la absorción y mejorar las propiedades optoelectrónicas, estructurales y morfológicas. A pesar de las buenas propiedades optoelectrónicas de las perovskitas de metilamonio, el catión orgánico disminuye su estabilidad, lo que llevó a investigar otros cationes inorgánicos. Las perovskitas de cesio son una alternativa prometedora, y por esta razón hemos sintetizado capas finas de perovskitas de cesio mixtas, CsPbBr3-xIx, para determinar los efectos que produce la sustitución parcial del yodo en las propiedades físicas y la estabilidad. Se obtuvieron capas con una buena resistencia a la humedad y temperatura, favoreciendo su aplicación en el campo fotovoltaico. Se ha estudiado la sustitución parcial del catión de metilamonio con otros cationes orgánicos, como el guanidinio e imidiazolio. Se demostró que pequeñas cantidades de guanidinio mejoran la estabilidad de las capas y su morfología. Se estableció el límite de solubilidad del guanidinio en el 20%, aproximadamente, y se determinó la estructura cristalina de las mezclas. La intensidad del pico de fotoluminiscencia aumentó para mezclas por debajo del límite de solubilidad. Se obtuvieron resultados similares para la sustitución del metilamonio con pequeñas cantidades de imidazolio. Los análisis de rayos X establecieron el límite de solubilidad en aproximadamente el 10% y una mejora en la cristalinidad. Los resultados de fotoluminiscencia sugieren que pequeñas cantidades de imidazolio reducen significativamente las recombinaciones no radiativas, actuando como un pasivador efectivo. Finalmente, se muestra el proceso de fabricación de dispositivos basados en MAPbI3 y sintetizados en función de las condiciones ambientales y empleando el dietil éter como anti-solvente. Los dispositivos mostraron una eficiencia máxima del 14.73%. Se ha probado que la oxidación del spiro-OMeTAD, bajo condiciones cont
[FR] Les perovskites orgàniques-inorgàniques de halurs de metilamoni i plom i les seues mescles han mostrat propietats optoelectròniques òptimes com a absorbent ideal per a aplicacions fotovoltaiques. Els dispositius solars basats en perovskita han evolucionat ràpidament, passant d'una eficiència del 3.9% en 2009, fins al 22.7% en 2017, i amb un cost de fabricació més baix que les cèl·lules solars de silici. No obstant això, un dels desavantatges de l'ús de absorbents de perovskita és la baixa estabilitat. En general, les cèl·lules que mostren un alt rendiment, perden la seua eficiència i es degraden ràpidament. Per a que aquestos materials puguen ser produits industrialment a gran escala és necessari estudiar-los en profunditat per millorar la eficiència i estabilitat. Una de les vies de millora és l'enginyeria composicional, estratègia que hem emprat en l'elaboració d'aquesta tesi i que consisteix en la investigació i la millora de les propietats optoelectròniques i morfològiques, derivades de la substitució i/o combinació de cations i anions, que constitueixen el material de perovskita. S'han sintetitzat pols purs de perovskita per a I, Br, Cl, a partir d'els quals es van preparar capes pures i mixtes MAPbX3-xYx per a millorar les propietats optoelectròniques i estructurals. Mitjançant anàlisi de difracció de raigs X, s'estudiaren les propietats estructurals del pols cristalins i capes pures i mixtes. Els anàlisis d'UV-vis i fotoluminiscència, mostren que el rang d'absorció varia al llarg de l'espectre visible en funció del contingut de l'halur. Les anàlisis de fotoluminiscència i calorimetria diferencial mostren els canvis de fase de les perovskites pures a diferents temperatures, coincidint aquestos canvis en totes dues anàlisis. L'anàlisi FESEM de les perovskites pures, mostra les diferències morfològiques entre els pols i capes. Seguint aquesta línia d'investigació, s'estudiaren les perovskites mixtes de iode-brom, amb un contingut de brom de fins el 33%, ajustant el bandgap per a evitar pèrdues en l'absorció i millorar les propietats optoelectròniques, estructurals i morfològiques. Malgrat les bones propietats optoelectròniques de les perovskites de metilamoni, el catió orgànic disminueix la estabilitat, la qual cosa ha portat a investigar l'ús d'altres cations inorgànics. Les perovskites de cesi són una alternativa prometedora, i per aquesta raó hem sintetitzat capes fines de perovskites de cesi mixtes, CsPbBr3-xIx, per tal de determinar els efectes de la substitució parcial del iode en les propietats físiques i l'estabilitat. Es van obtenir capes amb una bona resistència a la humitat i a la temperatura, afavorint la seua aplicació en el camp fotovoltaic. S'ha estudiat també la substitució parcial del catió de metilamoni amb altres cations orgànics, com el guanidini i imidiazoli. S'ha demostrat que petites quantitats de guanidini milloren l'estabilitat i la morfologia de les capes. S'ha establert que el límit de solubilitat del guanidini es del 20%, aproximadament, i s'ha determinat l'estructura cristal·lina de les mescles. S'ha observat un augment en la intensitat del pic de fotoluminiscència per a mescles per sota del límit de solubilitat. Es van obtenir resultats similars per a la substitució del metilamoni amb petites quantitats de imidazoli. Les anàlisis de difracció de raigs X van establir el límit de solubilitat en aproximadament el 10% i una millora en la cristalinitat. Els resultats de fotoluminiscència suggereixen que petites quantitats de imidazoli redueixen les recombinacions no radiatives, actuant com un pasivador efectiu. Finalment, es mostra el procés de fabricació de dispositius basats en MAPbI3 i sintetitzats en funció de les condicions ambientals, especialment la humitat relativa i utilitzant el dietil èter com anti-solvent. Els dispositius van mostrar una eficiència màx
[EN] Organic-inorganic methylammonium lead halides perovskites and their mixtures have shown optimal optoelectronic properties as an ideal absorber for photovoltaic applications. In the last decade, solar devices based on perovskite have evolved rapidly, going from an initial efficiency of only 3.9% in 2009, to an efficiency of 22.7% in 2017 and being, at the same time, more cost-effective than silicon solar cells. However, one of the main disadvantages when using perovskite absorbents in photovoltaic devices is their low stability. In general, cells that show high performance lose their efficiency and degrade rapidly. For these materials to be scalable it is necessary to carry out in-depth studies aiming at improved efficiency and stability. One of the main sources to improve stability and efficiency is compositional engineering, a strategy employed in the elaboration of this thesis, consisting of the investigation and improvement of the optoelectronic and morphological properties, derived from the substitution and / or combination of cations and anions, which constitute the perovskite material. Pure powders of perovskite were synthesized, for I, Br, Cl, from which pure and mixed MAPbX3-xYx films were prepared in order to improve their optoelectronic and structural properties. By means of X-ray diffraction analysis, the structural properties of crystalline powders and pure and mixed films were studied. Employing UV-vis and photoluminescence analysis, it was observed that the absorption range varied along the visible spectrum as a function of the halide content in the thin films. Both, photoluminescence and differential scanning calorimetry analysis showed the changes of phase of the pure perovskites at different temperatures. FESEM characterization of the pure perovskites showed the morphological differences between the powders and the films. Following this line of research, mixed perovskites of iodine-bromine with a bromine content of up to 33% were studied in more detail. The bandgap was tuned to avoid significant losses in absorption and improve the optoelectronic, structural and morphological properties. Despite the excellent optoelectronic properties of the methylammonium perovskite, the presence of the organic cation decreases its stability, which prompted research into the use of other inorganic cations. Cesium perovskites, are a very promising alternative, and for this reason we synthesized thin films of mixed cesium perovskites, CsPbBr3-xIx, to determine the effects of the partial substitution of iodine on physical properties and stability. Films with a very good resistance to moisture and temperature were obtained, which will favor the application of this type of perovskites in the photovoltaic field. The partial replacement of the methylammonium cation with other organic cations, such as guanidinium and imidiazolium, was also studied, showing that small amounts of guanidinium significantly improve the stability of the films and their morphology. It was established that the solubility limit of guanidinium is approximately 20%, and the crystalline structure of the mixtures was determined. An increase in the intensity of the photoluminescence peak for mixtures below the solubility limit was observed. Similar results were obtained for the substitution of methylammonium with small amounts of imidazolium. X-ray diffraction analyzes established the solubility limit at approximately 10% and an improvement in crystallinity. Photoluminescence results suggest that small amounts of imidazolium significantly reduce nonradiative recombinations, acting as an effective passivator. Finally, the manufacturing process of devices based on MAPbI3 and synthesized according to environmental conditions, especially relative humidity and using diethyl ether as anti-solvent is shown. The devices presented a maximum efficiency of 14.73%, proving that the oxidation of spiro-OMeTAD, under controlled humidity conditions, can improve efficiency.
Vega Fleitas, E. (2018). Study and Characterization of Hybrid Organic-Inorganic Perovskites for Solar Cells Applications [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/113402
TESIS

Le soleil offre une ressource abondante et inépuisable d’énergie. Le photovoltaïque est la technologie la plus importante pour rendre l'énergie solaire utilisable car les cellules solaires photovoltaïques recueillent le rayonnement solaire et le convertissent en énergie électrique. Les cellules solaires à colorant (DSSC) ont été très étudiées en raison de leur faible coût, d’une technique de fabrication facile et une grande versatilité. Un dispositif classique DSSC comprend une photo-anode à colorant, une contre-électrode et un électrolyte contenant un couple redox et des additifs. Pour améliorer la stabilité de ces dispositifs, le remplacement de l'électrolyte liquide par des matériaux solides transporteur de trous a été étudié pour donner ce que l’on appelle des cellules solaires à colorant solides (ssDSSCs). Récemment, les pérovskites hybrides organique/inorganiques ont été introduites dans les systèmes ssDSSCs comme absorbeur de lumière. Les cellules correspondantes, appelées cellules solaires à pérovskite (PSC) ont ouvert une nouvelle ère en photovoltaïque en raison du faible coût de ce matériau et la grande efficacité de ces cellules. L'efficacité de conversion de puissance a augmenté de 3,8% en 2009 à un rendement certifié de 20,1% fin 2014. Les composants des cellules solaires à pérovskite comprennent: une couche compacte d'oxyde jouant le rôle de barrière pour les trous photogénérés, une couche de transport des électrons (un semiconducteur de type n), la couche de l’absorbeur de lumière à base de pérovskite d’halogénure de plomb, la couche de transport des trous et le contact arrière. Dans cette thèse, nous nous sommes concentrés sur la préparation et l’amélioration des propriétés de la couche de transport d'électrons et la couche de pérovskite
Solar energy is one of the most important resources in our modern life. Photovoltaic is the most important technology to render the solar energy usable since photovoltaic solar cells harvest light coming from sun and convert sunlight into electrical energy. Dye sensitized solar cells have gained widespread attention due to their low cost, easy fabrication technique and tunable choice for the device. A traditional DSSC device includes a dye-sensitized photo-anode, a counter electrode and an electrolyte containing a redox couple system and additives. To improve the device stability, the liquid electrolyte replacement by a solid state hole transport material has been studied in so-called solid-state dye sensitized solar cells (ssDSSCs). Recently, an amazing light perovskite absorber was introduced into the ssDSSC system to replace the dye, opening the new field of research. Perovskite solar cells (PSCs) open a new era in photovoltaic due to the low cost of this material and the high efficiency of these cells. The power conversion efficiency has risen from 3.8% to a certified 20.1% within a few years. The components in the perovskite solar cell include: the compact metal oxide blocking layer, the electron transport layer, the lead halide perovskite layer, the hole transport layer and the back contact. In this thesis, we focused on the preparation and improving the properties of the electron transport layer and the perovskite layer

Solar cells involving two different perovskites were manufactured and analyzed. The perovskites were (CH3NH3)PbI3 and (CH3NH3)SnI3. Both perovskites have a shared methyl ammonium group (MA) and are used as both light absorbing material and hole conducting material (HTM) in this project. The preparation procedures for the complete device were according to previous attempts to make stable organic-inorganic hybrid perovskites and involved different layers and procedures. Both perovskites were manufactured by mixing methyl ammonium iodide with either lead iodide or tin iodide in different concentrations. This was then deposited on a 600nm thick mesoporous TiO2 layer. Deposition of the hole-transporting material (HTM) was done by spin-coating 2,2´,7,7´-tetrakis-(N,N-dip-methoxyphenylamine) 9,9´-spirobifluorene, also called spiro-OMeTAD. Lastly thermal evaporation was used to deposit a silver electrode. Different measurements were done on the light absorbing materials. The lead perovskite solar cell device was subjected to illumination with Air Mass 1.5 sunlight (100mW/cm2) which produced an open circuit voltage Voc of 0.645 V, a short circuit photocurrent Jsc of about 7 mA/cm2, and a fill factor FF of 0.445. This resulted in a power conversion efficiency (PCE) of about 2% and an incident photon to current efficiency (IPCE) of up to 60%. The tin perovskite has not been used in solar cells before and the initial results presented here shows low performance using the same device construction as for the lead perovskite. However, the incident photon to electron conversion affirms that there is a current in the visible region, and IPCE of 12.5 % was observed at 375nm. UV-visible NIR measurement was used to analyze the light absorption of the perovskite structures and a broader light absorption was observed for the lead perovskite compared to the tin perovskite. X-ray diffraction (XRD) analyzing was done on both perovskite materials using different concentrations and both with and without nanoporous TiO2 film. Both perovskites demonstrate very similar peaks with some exceptions. Photo-induced absorption (PIA) measurement was used for the purpose of showing the magnitude of charge separation or hole transfer in the light absorbing material, both when using the perovskites as a light absorber and a hole conductor. This is measured by analyzing the hole injection from the excited light absorber into the HTM. Hole transfer was observed for the lead perovskite (when used as light absorber) and tin perovskite (when used as hole conductor).

Hybrid organic-inorganic solar photovoltaic (PV) cells capable of directly converting sunlight to electricity have attracted much attention in recent years. Despite evident technological advancements in the PV industry, the widespread commercialisation of solar cells is still being mired by their low conversion efficiencies and high cost per Watt. Perovskites are an emerging class of semiconductors providing a low-cost alternative to silicon-based photovoltaic cells, which currently dominate the market. This thesis develops a series of studies on “all-solid state perovskite solar cells” fabricated via vapour deposition which is an industrially-accessible technique, to achieve planar heterojunction architectures and efficient PV devices. Chapter 2 presents a general outlook on the operating principles of solar cells, delving deeper into the specific operational mechanism of perovskite solar cells. It also explores the usual methods employed in the fabrication of perovskite thin films. Chapter 3 describes the experimental procedures followed during the fabrication of the individual components constituting the device from the synthesis of the precursors to the construction of the functioning perovskite PV devices. Chapter 4 demonstrates pioneering work involving the dual-source vapour deposition (DSVD) of planar heterojunction perovskite solar cells which generated remarkable power conversion efficiency values surpassing 15%. These significant results pave the way for the mass-production of perovskite PVs. To further expand the range of feasible vapour deposition techniques, a two-layer sequential vapour deposition (SVD) technique is explored in Chapter 5. This chapter focusses on identifying the factors affecting the fundamental properties of the vapour-deposited films. Findings provide an improved understanding of the effects of precursor compositions and annealing conditions on the films. Chapter 5 concludes with a comparison between SVD and DSVD fabricated films, highlighting the benefits of each vapour deposition technique. Furthermore, hysteretic effects are analysed in Chapter 6 for the perovskite PV devices fabricated based on different structural configurations. An interesting discovery involving the temporary functioning of compact layer-free perovskite PV devices suggests the presence of a built-in-field responsible for the hysteresis of the cells. The observations made in this chapter yield a new understanding of the functionality of individual cell layers. Combining the advantages of the optimum vapour deposition technique established in Chapter 4 and Chapter 5, with the enhanced understanding of perovskite PV cell operational mechanism acquired from Chapter 6, an ongoing study on an “all-perovskite” tandem solar cell is introduced in Chapter 7. This demonstration of the “all-perovskite” tandem devices confirms the versatility of perovskites for a broader range of PV applications.

L'objectif de cette thèse était l’étude de dispositifs électroniques à base de pérovskites hybrides. Dans ce cadre nous avons développé et fabriqué des transistors à effet de champ (FET) ainsi que des cellules solaires à base de perovskite. Dans le cas des transistors, en utilisant des couches minces de pérovskites hybride hautement cristallisées nous avons réalisé des transistors ambipolaires fonctionnant à la température ambiante et présentant une hystérésis faible, une transconductance élevée (pour ce type de matériau), et un rapport Ion / Ioff> 104. Dans le cadre de cette thèse l’utilisation de plusieurs diélectriques nous a permis d’obtenir une forte modulation de la conductance du canal avec des tensions de grille relativement faibles (4-6V). Dans ce cadre l’oxyde d’Hafnium de permittivité relative er=23.5 a montré de très bonnes performances et une très bonne compatibilité pour la croissance de pérovskite hybride. Après plusieurs étapes de polarisation les dispositifs ont présenté un fonctionnement stabilisé et ont été mesurés au cours des cycles consécutifs pendant 14 heures avec peu de changement dans leurs performances. Nous avons mis en évidence que l’augmentation du champ électrique a permis la formation d’un canal de trous à l’interface. La polarisation consécutive des dispositifs à base de HfO2/pérovskite a amené à la création d’un second courant d’électrons et a mis en évidence un fonctionnement ambipolaire final. L’ensemble des dispositifs ont présenté une hystérésis dont l’amplitude était parfois non négligeable. Cela a démontré la présence de charges mobiles ioniques aux interfaces qui influence les courants de sorties du dispositif. Dans la dernière partie de la thèse nous nous sommes intéressés à la croissance de pérovskite hybride pour la production de cellules solaires. Nous avons étudié les deux conditions de croissance suivantes : conditions sous air normal (humidité relative> 60%) et en atmosphère d’azote en boites à gants (humidité relative <0.1 ppm). Par ces deux voies nous avons obtenu respectivement des rendements de conversion photovoltaïque respectivement de 5% et 8%
The objective of this thesis was the study of electronic devices based on hybrid perovskites. In this context we have developed and produce field effect transistors (FETs) and solar cells based on hybrid perovskite material. In the case of transistors, using thin layers of highly crystallized hybrid perovskites we have made ambipolar transistors operating at room temperature and having low hysteresis, high transconductance (for this type of material) and a ratio of Ion / Ioff > 104. In the context of this thesis, the use of several dielectrics allowed us to obtain a high modulation of the channel conductance with relatively low gate voltages (4-6V). Hafnium oxide with relative permittivity er = 23.5 showed very good performances and a very good compatibility for the hybrid perovskite growth. After several polarization steps the devices exhibited stabilized operation and were measured in consecutive cycles for 14 hours with small change in their performance. We have shown that the increase of the electric field allowed the formation of a hole channel at the interface. The successive polarization of HfO2 / perovskite-based devices led to the creation of a second electron current and demonstrated a final ambipolar device. All the devices presented a hysteresis with amplitude sometimes not negligible. This demonstrated the presence of mobile ion charges at the interfaces that influence the output currents of the device. In the last part of the thesis we focused our work in hybrid perovskite growth for the production of solar cells. We have studied two growth conditions: conditions under normal air (relative humidity> 60%) and nitrogen atmosphere in glove boxes (relative humidity <0.1 ppm). By these two paths we obtained photovoltaic conversion efficiencies of 5% and 8% respectively

Les cellules solaires pérovskites hybrides ont marqué le monde du photovoltaïque avec une augmentation spectaculaire des rendements durant ces quatre dernières années. Avec des rendements dépassant 20% à l’heure actuelle, ce type de cellules suscite une attention particulière dans le monde scientifique. Dans l’architecture de la cellule solaire pérovskite, le TiO2 est l’oxyde le plus utilisé comme matériau collecteur d’électrons. Cette couche d’oxyde joue un rôle important dans la cellule, cependant le procédé d’élaboration du TiO2 requiert une étape de recuit à haute température. En plus des coûts élevés de production qu’elle implique, son utilisation exclut son application aux substrats sensibles aux hautes températures tels que les substrats plastiques flexibles par exemple.Cette thèse est centrée sur le remplacement du TiO2 par le ZnO en tant que couche collectrice d’électrons et bloqueuse de trous. Ce matériau représente une alternative intéressante en raison de ces propriétés comparables et même supérieures à celles du TiO2. L’intérêt du choix du ZnO réside dans sa simplicité de mise en œuvre. Ce matériau peut en effet être synthétisé à basse température (<100°C) et sous différentes structures. Dans cette étude nous avons fait le choix de considérer les croissances de ZnO par voie électrochimique et par pulvérisation cathodique. Dans des conditions de dépôts optimisées des couches de pérovskite et de ZnO, des rendements record de 14.2% et 9.7% ont été obtenus dans des architectures plane et nanostructurée respectivement
Perovskite solar cells have marked the photovoltaic world with a spectacular increase of efficiencies over the last four years. With efficiencies exceeding 20%, this type of solar cells attracts a particular attention in the photovoltaic field. In the standard perovskite solar cell stack, TiO2 is used as an electron-collecting layer. This oxide layer plays an important role in the cell, however, its growth process requires a high temperature annealing step. In addition to the high production costs involved, its use also exclude its application to temperatures sensitive substrates such as flexible plastic materials.This thesis focuses on the replacement of the TiO2 bilayer by a ZnO electron-collecting and hole-blocking layer. We consider ZnO as an alternative to its comparable and even superior properties. One of the interests of the choice of ZnO lies in its simplicity of implementation and the possibility to synthesize it at low temperature (<100°C) and under different structures. The ZnO is here synthesized by electrochemical way and sputtering process. Under optimized deposition conditions of perovskite and ZnO layers, record efficiencies of 14.2% and 9.7% have been obtained in planar and nanostructured architecture respectively

This thesis consists of three main studies: magnetic field effects in thermally activated delayed fluorescent (TADF) organic light emitting diodes (OLEDs), magnetic field effects in bipolar and unipolar polythiophene (P3HT) devices and a study of hybrid organic/inorganic perovskite devices. Spin-dependent transport and recombination processes of spin-pair species have been detected by magnetic field effect (MFE) technique in carbon-based semi- conductor devices. Magneto-electroluminescence (MEL) and magneto-conductivity have been measured as a function of the applied magnetic field, B, in light emitting diodes. TADF materials have been used instead of simple fluorescent materials in OLEDs. We have observed very large magnetic response with TADF materials. The second study is magnetic field effects of regio-regular P3HT based OLED devices. P3HT is a well known semiconducting polymer, and its electrical properties such as magneto-conductance can be affected by an applied magnetic field. P3HT was chosen because it exhibits a sign change in magnetoresistance (MR) as the bias is increased. Unipolar and bipolar devices have been fabricated with different electrode materials to understand which model can be best to explain organic magnetoresistance effect, possibly depending on the operating regime of the device. Transport and luminescence spectroscopies were studied to isolate the different mechanisms and identify their fingerprints. The third study is on hybrid organic-inorganic perovskite devices. With the potential of achieving very high efficiencies and the very low production costs, perovskite solar cells have become commercially attractive. Scanning electron microscopy (SEM) images and absorption spectrum of the films were compared in single-step solution, two-step solution and solution-assisted vapor deposition techniques. Grain size, morphology and thickness parameters of perovskite films were studied within these techniques. Perovskite solar cells were fabricated and their efficiencies were measured.

Perovskite-solceller är en framväxande och lovande tunnfilmsteknik, som uppnådde hög effektivitet på en ofantlig kort tid. Den nuvarande arkitekturen i cellen, som innefattar titanoxid och Spiro-OMeTAD (en organisk förening) som laddningstransportlager (CTL), saknar stabilitet och visar hysteretiskt beteende. För att bedöma dessa stora problem utvecklas oorganiska CTL i PV-samhället. I detta arbete utförs en grundlig översyn av litteraturen om dessa oorganiska CTL. Fyra av dem identifieras som bra kandidater på grund av de höga prestanda de uppnådde och deras kemiska stabilitet: SnO2, ZnO, CuSCN och NiO. Betydelsen av gränssnitten i denna typ av cell visas också. Numerisk simulering av CTLs utförs också med ett dedikerat 1D-modelleringsverktyg (SCAPS), vilket gör att vi kan föreslå viktiga parametrar för att optimera i en CTL. Slutligen studeras effekterna av gränssnittet på prestanda hos en perovskit-solcell med hyperspektral avbildning av cellens fotoluminescensrespons. Med hjälp av en korrekt passningsalgoritm ger denna icke-destruktiva metod insikt om de opto-elektroniska egenskaperna hos perovskiten som odlas på olika substrat.
Perovskite solar cells are an emerging and promising thin film technology, which reached high efficiencies in an unprecedented short time. However, the current architecture of the cell, which includes titanium oxide and Spiro-OMeTAD (an organic compound) as charge transport layers (CTLs), lacks stability and shows hysteretic behavior. In order to assess these major issues, inorganic CTLs are developed in the PV community. This work performs a thorough review of the literature regarding these inorganic CTLs. Four of them are identified as good candidates because of the high performances they reached, and of their chemical stability: SnO2, ZnO, CuSCN and NiO. The significance of the interfaces in this kind of cell is also demonstrated.  Numerical simulation of CTLs is also performed using a dedicated 1D modelisation tool (SCAPS), which allows us to propose key parameters to optimize in a CTL. Finally, the effects of the interface on the performances of a perovskite solar cell are studied with hyperspectral imaging of photoluminescence response of the cell. Using a proper fit algorithm, this non-destructive method gives insight into the opto-electronic properties of the perovskite grown on different substrates.

Der Schwerpunkt der vorliegenden Arbeit liegt in der Charakterisierung der elektronischen Eigenschaften von hybriden organisch-anorganischen Perowskit (HOIP)-Schichten während der Schichtbildung und in verschiedenen Umgebungen mittels Photoelektronenspektroskopie (PES). Insbesondere wird der Methylammonium-Blei-Iodid-Chlorid-Perowskit (MAPbI3-xClx) untersucht. Als erstes werden Änderungen in den elektronischen Eigenschaften, der Zusammensetzung, sowie der Kristallstruktur mittels PES, Flugzeit-Sekundärionenmassenspektrometrie, sowie Röntgendiffraktometrie mit streifendem Einfall analysiert. Die Resultate weisen auf die entscheidende Rolle von Chlor im texturierten Wachstum der Perowskitschicht hin. Die auskristallisierte Perowskitschicht weist eine stärkere n-Typ Eigenschaft auf, welche auf die Änderung der Zusammensetzung während der Schichtbildung zurückgeführt werden kann. Außerdem beweisen die Ergebnisse eindeutig die Ablagerung von Chlor an der Grenzfläche zwischen der Perowskitschicht und dem Substrat. Zweitens werden die separaten Einflüsse von Wasser, Sauerstoff, und Umgebungsluft auf die elektronischen Eigenschaften von MAPbI3-xClx-Schichtoberflächen untersucht. Bereits geringste Wassermengen ähnlich wie im Hochvakuum oder in inerter Umgebung können eine reversible Reduzierung der Austrittsarbeit hervorrufen. Höherer Wasserdampf-Partialdruck führt zu einer Verschiebung des Valenzbandmaximums (VBM) weit vom Fermi-Niveau, sowie zu einer Reduzierung der Austrittsarbeit. Im Gegensatz dazu führt eine Sauerstoffexposition zu einer Verschiebung des VBM in Richtung des Fermi-Niveaus und zu einer Steigerung der Austrittsarbeit. Analog kommt es zu einer Verschiebung von bis zu 0.6 eV bei einer Exposition gegenüber Umgebungsluft, was den vorwiegenden Einfluss von Sauerstoff demonstriert. Die vorliegenden Untersuchungen betonen den kritischen Einfluss der Schichtbildung, der Zusammensetzung, sowie der Umgebungsbedingungen auf die elektronischen Eigenschaften von HOIP.
The present thesis aims at characterizing the electronic properties of solution-processed hybrid organic-inorganic perovskites (HOIPs) in general, and the HOIP methyl ammonium (MA) lead iodide-chloride (MAPbI3-xClx) films, in particular, at different stages, namely from its formation to its degradation, by means of photoelectron spectroscopy (PES). Firstly, the formation of MAPbI3-xClx films upon thermal annealing is monitored by a combination of PES, time-of-flight secondary ion mass spectrometry, and grazing incidence X-ray diffraction for disclosing changes in electronic properties, film composition, and crystal structure, respectively. Overall, the results point to the essential mediating role of chlorine in the formation of a highly textured perovskite film. The film formation is accompanied by a change of composition which leads to the film becoming more n-type. The accumulation of chlorine at the interface between perovskite and the underlying substrate is also unambiguously revealed. Secondly, the separate effects of water and oxygen on the electronic properties of MAPbI3-xClx film surfaces are investigated by PES. Already low water exposure – as encountered in high vacuum or inert conditions – appears to reversibly impact the work function of the film surfaces. Water vapor in the mbar range induces a shift of the valence band maximum (VBM) away from the Fermi level accompanied by a decrease of the work function. In contrast, oxygen leads to a VBM shift towards the Fermi level and a concomitant increase of the work function. The effect of oxygen is found to predominate in ambient air with an associated shift of the energy levels by up to 0.6 eV. Overall, the findings contribute to an improved understanding of the structure-property relationships of HOIPs and emphasize the impact of least variation in the environmental conditions on the reproducibility of the electronic properties of perovskite materials.

Hybrid lead halide perovskites, AMX 3 compounds in which A = CH 3 NH 3 (MA), CH(NH 2 ) 2(FA), Cs; M = Pb,Sn; X = I, Br, Cl, display remarkable performance in solution-processed optoelectronic devices, including > 22% efficient thin film photovoltaic cells. These compounds represent the first class of materials discovered to exhibit properties associated with high performance compound semiconductors, while being formed at or near room temperature using simple solution chemistry techniques. This thesis is focused on the synthesis, structural characterisation and phase behaviour of MAPbI 3 , FAPbI 3 , A-site solid solutions and novel organic metal halide framework materials. The complete atomic structure and phase behaviour of methylammonium lead iodide is elucidated for the first time, including hydrogen positions, using high flux, constant wave-length neutron powder diffraction. At 100 K an orthorhombic phase, space group Pnma, is observed, with the methylammonium cations ordered as the C–N bond direction alternates in adjacent inorganic cages. Above 165 K a first order phase transition to tetragonal, I4/mcm, occurs with the unlocking of cation rotation, which is disordered primarily in the ab plane. Above 327 K a cubic phase, space group Pm3m, is formed, with the cations isotropically disordered on the timescale of the crystallographic experiment. The high temperature phase of formamidinium lead iodide, α-FAPbI 3 is shown for the first time to be cubic, (Pm3m), at room temperature using time-of-flight, high resolution neutron powder diffraction. Polymorphism and the low temperature phase behaviour of FAPbI 3 have been further investigated using reactor and spallation neutron sources with high resolution in temperature. A tetragonal phase, P4/mbm, is confirmed in the temperature range 140-285 K.The composition, structural and optical parameters of ’A’ site solid solutions (MA/FA)PbI 3 have been investigated by single crystal X-ray diffraction, UV-vis spectroscopy and 1 H solution NMR. A composition-dependent transition in the crystal class from tetragonal to cubic(or pseudo-cubic) at room temperature is identified and correlated to trends in the optical absorption. Novel hybrid materials with inorganic frameworks of varying dimensionality from 0D to 2D, including imidazolium lead iodide and piperazinium lead iodide, have been synthesised using various templating organic cations and their atomic structures solved by single crystal X-ray diffraction.

The work documented in this thesis concerns the control and modification of semiconducting perovskite thin films for their use in perovksite solar cells (PSCs). PSCs are a promising new thin-film technology, offering both high solar to electricity conversion efficiencies and cheap fabrication costs. Herein, the boundaries of perovskite solar cell research are pushed further by tackling several challenges important to the field. Initially, this work focuses on understanding why the best PSCs made so far have been mesostructured devices, with the perovskite infiltrated into a scaffold. It is shown that this can be seen as simply a fabrication aid; without the scaffold, thin films easily dewet from the substrate. By understanding the crucial parameters important in carefully controlling this dewetting, it is minimised, and it is shown that scaffold-free planar heterojunction devices with high efficiencies can be fabricated. This work leads on to the next section; the development of semi-transparent perovskite solar cells. In their present state, PSCs cannot compete with silicon as stand-alone modules. Here, the morphological control has been leveraged to realise a different embodiment – semi-transparent perovskite devices for use in building-integrated photovoltaics. Competitive efficiency and transparency are demonstrated. Moreover, a hybrid self-tinting power-generating window concept is fabricated, by combining the photovoltaic and electrochromic technologies. In the third section of the thesis, the limitations of the most studied perovskite material, methylammonium lead halide, are addressed: its overly wide bandgap and thermal instability. To address these, the chemical constituents of the perovksite are altered, and the development of more efficient and more stable materials are reported. These are likely to be important for perovskite modules to pass international certification requirements for commercialisation. Finally, an in-depth study on the effect of ambient moisture, relevant for considering scale-up and the fabrication environment needed, is carried out. It is shown that the presence of some moisture during film fabrication allows a reduction of defect states in the perovskite material, enhancing device performance and film quality.

This thesis details the development of a novel photovoltaic device based on organometal halide perovskites. The initial focus of this thesis begins with the study of lighttrapping strategies in solid-state dye-sensitised solar cells (detailed in chapter 3). While I report enhancement in device performance through the application of near and far-field light-trapping techniques, I find that improvements remain step-wise due to fundamental limitations currently employed in dye-sensitised solar cell technology— notably, the available light-sensitising materials. I found a promising yet under researched family of materials in the methyl ammonium tri-halide plumbate perovskite (detailed in chapter 4). The perovskite light-sensitiser was applied to the traditional mesoscopic sensitised solar cell device architecture as a replacement to conventional dye yielding world-record breaking photo-conversion e!ciencies for solid-state sensitised solar cells as high as 8.5%. The system was further developed leading to the conception of a novel device architecture, termed the mesoporous superstructured solar cell (MSSC), this new architecture replaces the conventional mesoporous titanium dioxide semiconductor with a porous insulating oxide in aluminium oxide, resulting in very low fundamental losses evidenced through high photo-generated open-circuit voltages of over 1.1 V. This development has delivered striking photo-conversion ef- ficiencies of 10.9% (detailed in chapter 6).

Perovskite photovoltaics is one of the fastest growing opto-electronic technologies with device efficiencies currently exceeding 23%. The opportunity to deposit these abundant materials with large area solution processing techniques could make perovskites viable for low-cost production. However, since perovskite materials are prone to degradation, their lifetime needs to be improved to that of silicon solar cells before these devices can be commercialized. Moreover, unlike most semiconductors, trap densities in polycrystalline perovskite films in high-performing devices have been determined to be relatively large, suggesting a remarkable defect tolerance in perovskite films that needs to be understood in the context of the nature of the trap states and any residual non- radiative losses. These non-radiative losses are observed as photoluminescence heterogeneity within perovskite films, even for high-performing perovskite systems. In this work, we explore the degradation kinetics of perovskite devices under stress conditions and find that further stability improvements should focus on the mitigation of trap generation during ageing. Furthermore, we fabricate perovskite solar cells with a novel back-contact structure, in which electron- and hole-selective electrodes are co-positioned on the back side of the cell and spaced by 100 μm. By utilising grazing-incidence X-ray diffraction, we show that even in the earliest stages of conversion of precursors to perovskite we achieve remarkably high open-circuit voltages, suggesting that the defect tolerance of perovskites appears at an early stage in the conversion process. Moreover, we employ scanning X-ray diffraction with nanofocused beam and obtain detailed information, revealing overlapping grains located at different depths within perovskite films. We find that the critical grain size is the longer-range structural super-grains rather than the grains viewed with conventional microscopy techniques. These findings further highlight the presence of structural defects in perovskite materials and provide important insights towards improving the optoelectronic behaviour of these materials.

In the present work, anomalous distortions occurring in the current-voltage characteristic of perovskite solar cells (PSCs), usually called J-V curve hysteresis, are studied by several methods. This includes dynamic direct current (DC) mode J-V experiments and impedance spectroscopy (IS) analyses in dark and under illumination. The J-V curves of PSCs were measured under different conditions showing capacitive hysteretic currents. This is related with low frequency excess capacitance in the IS spectra. These two features are correlated with the response of mobile ions in space charge regions close to the interfaces. The large values of capacitance under illumination in the sub-Hz regime were explained in terms of mobile ions space charges and chemical capacitances assuming a proportionality between the number of ionized/activated mobile ions and the concentration of charge carriers and photon fluence.
En el presente trabajo se estudian por varios métodos las distorsiones anómalas en la característica de corriente-voltaje de las celdas solares de perovskita (PSC), típicamente llamada histéresis de J-V. Esto incluye experimentos dinámicos de J-V en modo de corriente continua (DC) y análisis de espectroscopía de impedancia (IS) en oscuridad y bajo iluminación. Las curvas J-V en oscuridad de las PSCs exhiben corrientes capacitivas, relacionadas con un exceso de capacitancia de baja frecuencia en los espectros de IS. Estas dos características están correlacionadas con la respuesta de iones móviles en regiones espaciales de carga hacia las interfaces. Los grandes valores de capacitancia bajo iluminación a frecuencias por debajo de las unidades de Hz se explicaron en términos de regiones de cargas espaciales de iones móviles y capacitancias químicas, suponiendo una proporcionalidad entre el número de iones móviles ionizados/activados y la concentración de portadores de carga y flujo de fotones.

In the last 10 years, the research interest has been drawn towards the hybrid organic-inorganic halide perovskites, an innovative material characterized by remarkable optoelectronic properties and by its simplicity of fabrication; hybrid halide perovskites are currently being employed as active material in solar cells, X-ray photodetectors and light emitting devices. The following thesis presents the characterization of two perovskite-based materials. The first is a methylammonium lead iodide (MAPbI3) thin film solar cell, which has been fabricated and characterized at the University of Konstanz (Germany), with the aim to optimize the deposition procedure. The second material is a methylammonium lead bromide (MAPbBr3) single crystal that have been characterized at the University of Bologna with surface photovoltage and photocurrent spectroscopies, as a function of the deposited dose of X-rays in order to monitor the induced effects of radiation. After the exposure to X-rays, the exciton binding energy, calculated from the surface photovoltage spectra, has been found to increase by 20 meV with respect to the not irradiated sample. A similar result has been found with the photocurrent spectroscopy. The reasons for the increase in binding energy is discussed and attributed to a change in polarizability of the single crystal. The recovery of the crystals has been registered as well and has shown that the material is able to return to the initial condition after just few hours from the last X-ray's deposition.

La thèse a pour but d’élaborer et d’étudier les potentialités des semi-conducteurs organiques, transporteurs de trous (HTMs) pour l’application photovoltaïque à l’aide de cellules solaires à base de pérovskite (PSCs). Plusieurs familles de molécules HTM ont été préparées et déposées en solution pour l’élaboration des cellules solaires. L'objectif principal étant d'étudier et d’apporter des informations sur la relation entre la structure moléculaire des nouveaux matériaux de transport de trous et les performances photovoltaïques obtenues, cette étude contribue à une meilleure compréhension fondamentale des propriétés requises des matériaux de transport de trous pour de meilleures performances photovoltaïques.La première étude concerne l’élaboration d’une molécule de type p à base de thieno [3,2-b] thiophène comme élément central avec des dérivés de dimethoxytriphenylamine comme donneurs d’électrons aux extrémités. Différentes conformations sont proposées et révèlent des performances photovoltaïques significativement différentes dans les dispositifs PSC. Notons par exemple, qu’une conformation de structure planaire favorisent la conjugaison avec des valeurs élevées de mobilités et conductivités obtenues.Dans la seconde étude, des molécules donneur-accepteurs à base de dérivés d’acridone 9 (10H) comme accepteur ont été élaborés. En y associant différents fragments donneurs d'électrons, on obtient des structures présentant des caractéristiques favorables à la fois pour de bons transferts de charge intramoléculaire (ICT) et des niveaux d’énergie HOMO-LUMO adaptés et favorisant l’injection des trous de la pérovskite vers l’électrode métallique via le HTM. Des études similaires ont été effectuées avec la thioxanthone.A partir d’un précurseur bon marché et d’une préparation aisée, la troisième étude a permis de synthétiser un dérivé de 9,9’-biacridone, molécule push-pull de type p révélant une structure tridimensionnelle, similaire à celle du Spiro-OMeTAD, molécule référence pour les PSCs.Enfin, la dernière étude concerne l’élaboration de molécules donneur-accepteur à base de thiéno [3,4-c] pyrrole-4,6-dione (TPD). La motivation de cette partie est le développement de la molécule à structure planaire améliorant l’empilement π-π dans la fabrication de dispositifs sans joints de grains. Ces molécules possèdent également un fort caractère ICT, une conjugaison π étendue sur toute la structure et une bonne solubilité ce qui en fait un candidat HTM idéal pour la réalisation d’un dispositif PSCs sans dopant
The aim of the thesis is to develop and study the potential of organic hole transporting materials (HTMs) for photovoltaic applications using perovskite-based solar cells (PSCs). Several families of HTM molecules have been prepared and deposited in solution for the fabrication of solar cells. Since the main objective is to study and provide information on the relationship between the molecular structure of new hole transport materials and the photovoltaic performances obtained, this study contributes to a better fundamental understanding of the required properties of hole transport materials for better photovoltaic performance.The first study concerns the development of p-type molecules based on Thieno [3,2-b] thiophene as a central unit and π-linker with dimethoxytriphenylamine as end-capping electron donors. Different configurations are designed and revealed significantly different photovoltaic performances in the PSC devices. Remarkable, a planar structure with linear conjugation shows higher values of mobility and conductivity than others, thus it improved device performances.In the second study, donor-acceptor molecules based on 9(10H)Acridone derivatives as an acceptor were developed. By incorporating different electron-donating fragments, we obtain structures with favorable characteristics for both good intramolecular charge transfer (ICT) character and adequate HOMO-LUMO energy levels. Their energy levels are suitable for collecting and injecting the holes from perovskite to the metal electrode through the HTM. Similar studies have been done with Thioxanthone.Using a cheap precursor and facile preparation, the third study synthesized a 9.9'-biacridone derivative. These p-type molecules possess a three-dimensional structure which is similar to that of Spiro-OMeTAD, state-of-the-art molecule for PSCs.Finally, the last study focus on the development of donor-acceptor molecules based on thieno [3,4-c] pyrrole-4,6-dione (TPD). The objective is elaboration of the planar structure molecule which could be improved the π-π stacking effect in the device fabrication without grain boundaries. These molecules also own a strong ICT character, an extended π-conjugation on the whole structure and a good solubility which makes it an ideal candidate for the dopant-free HTM in PSCs

Metallhalogenid-Perowskite (MHPs) sind Halbleiter, die einzigartige photophysikalische Eigenschaften aufweisen, die sie ideal für photovoltaische Anwendungen machen. Techniken werden kontinuierlich entwickelt, um die Leistungsgrenzen der Perowskite weiter zu verschieben. Dennoch weisen diese Materialien verschiedene Herausforderungen auf. Zu diesen gehören eine geringe Stabilität unter einer Vielzahl von äußeren Bedingungen, sowie eine große Diskrepanz zwischen den Wirkungsgraden von Geräten im Labormaßstab und großflächigen Geräten. Zunächst wurden mit Hilfe von Photolumineszenz-Spektroskopie Ladungsübertragungsmechanismen zwischen MHPs und atmosphärischen Gasen untersucht, um deren Einfluss auf die Materialstabilität zu bestimmen. Durch den Vergleich der Emission von verschiedene MHP wurde die Wirkung untersucht, die atmosphärische Gase auf Grenzdefekte im Material haben. Diese Löschungseffekte wurden nachfolgend mit dem Stern-Volmer-Modell analysiert. Es stellte sich heraus, dass ein Teil von der Gase bindet jedoch an die MHPs, wobei teilweise Kristalldefekte passiviert werden und für jedes der Gase Ladungstransfermechanismen vorgeschlagen wurden. Zweitens wurde die Skalierung von MHP-Bauelementen mittels Tintenstrahldruck untersucht. Dazu wurden drei Kristallisationstechniken ausgewertet. Eine davon verwendete eine sequenzielle Abscheidung von zwei Präkursortinten, während die beiden anderen kristallisierte Tinten verwendeten, die in einem Schritt abgeschieden wurden. Die letztgenannten Techniken verwendeten beide niedrige Drücke und bei einer wurde ein kontrollierter Stickstoffstrom auf die Probe angewendet. Solarzellen mit einer Effizienz von 16,8% auf einer Fläche von 0,16 cm² wurden demonstriert. Diese Ergebnisse zeigen ein neuartiges Verfahren zur Untersuchung von strahlungslosen Verlustwegen in MHPs auf. Zusätzlich demonstrieren diese Studien, dass der Tintenstrahldruck eine geeignete Technologie ist, um MHP-Bauelemente zu skalieren.
Metal halide perovskites (MHPs) are semiconductor materials that show unique photophysical properties, making them ideal for photovoltaic applications. Having shown power conversion efficiencies of up to 25.5%, techniques are continuously being developed to push perovskites to unprecedent limits. Yet, these materials present challenges like a low stability under a variety of conditions as well as a large disparity between the efficiencies of lab scale and large area devices. This thesis addresses these two major obstacles. First, charge transfer mechanisms between MHPs and atmospheric gases were studied to determine their effect on the material stability by using photoluminescence spectroscopy. By comparing the emission of MHPs, the effect that molecular oxygen, nitrogen, argon, and water have on boundary defects in the material was studied. These quenching effects were later analyzed using the Stern-Volmer model. It was found that the gases bounce off the surface, but a portion of them bind to the MHPs, in occasions passivating defects on the crystals. Using these results, charge transfer mechanisms were proposed for each one of the gases. Second, scaling of MHP devices was examined using inkjet printing. For this, three crystallization techniques were evaluated. One of them used sequential deposition of two precursor inks, while the other two crystallized ink that was deposited in one step. Both latter techniques used low pressures, below 1 mbar, and only one of them applied a controlled stream of nitrogen to the sample. Using these techniques, the deposition of a 15x15 cm² area as well as a device with an efficiency of 16.8% on an area of 0.16 cm² were demonstrated. These results show a novel procedure to study non-radiative loss paths in MHPs to enhance their stability and performance as devices. Also, they show that inkjet printing is a favorable technology to scale MHP devices and eventually facilitate the mass production of this type of photovoltaic devices.

Solar cells based on organohalide perovskites (PSCs) have made rapid progress in recent years and are a promising emerging technology. An important next evolutionary step for PSCs is their up-scaling to commercially relevant dimensions. The main challenges in scaling PSCs to be compatible with current c-Si cells are related to the limited conductivity of the transparent electrode, and the processing of a uniform and defect-free organohalide perovskite layer over large areas. In this work we present a generic and simple approach to realizing efficient solution-processed, monolithic solar cells based on methylammonium lead iodide (CH₃NH₃PbI₃). Our devices have an aperture area of 25 cm² without relying on an interconnected strip design, therefore reducing the complexity of the fabrication process and enhancing compatibility with the c-Si cell geometry. We utilize simple aluminum grid lines to increase the conductivity of the transparent electrode. These grid lines were exposed to an UV-ozone plasma to grow a thin aluminum oxide layer. This dramatically improves the wetting and film forming of the organohalide perovskite junction on top of the lines, reducing the probability of short circuits between the grid and the top electrode. The best devices employing these modified grids achieved power conversion efficiencies of up to 6.8%.

Ce travail de thèse a pour sujet la conception des cellules solaires photovoltaïques à base de pérovskite hybride par le biais de la technologie d’impression jet d’encre. Les deux premiers chapitres font la présentation du contexte de la thèse, à savoir l’alimentation d’un réseau autonome de capteurs, et passent en revue les aspects scientifiques des technologies jet d’encre et photovoltaïque de nouvelle génération. Le troisième chapitre présente la mise au point d’une cellule photovoltaïque à l’état de l’art et son évolution vers une architecture imprimable à basse température de recuit. La problématique de la stabilité des cellules photovoltaïques à pérovskite est aussi abordée. La dernière partie présente les différents aspects et problématiques de l’impression par jet d’encre des trois couches internes d’une cellule solaire pérovskite. Au terme de ce travail la possibilité d’imprimer des cellules solaires pérovskites avec des rendements supérieurs à 10 % a été démontrée, le tout en condition ambiante et à basse température
This thesis is about the design of photovoltaic solar cells based on hybrid perovskite using inkjet printing technology. The first two chapters present the context of the thesis, namely the powering of an autonomous sensor network, and review the scientific aspects of inkjet and photovoltaic technologies. The third chapter presents the development of a state-of-the-art photovoltaic cell and its evolution towards a printable architecture at low annealing temperatures. The problem of the stability of photovoltaic cells with perovskite is also discussed. The last part presents the different aspects and problems of the inkjet printing of the three inner layers of a perovskite solar cell. At the end of this work the possibility of printing perovskite solar cells with efficiencies higher than 10% has been demonstrated, all in ambient conditions and at low temperature

Les pérovskites hybrides halogénées (ABX3) sont utilisées depuis cinq ans comme couches absorbantes pour de nouvelles cellules solaires à bas coût combinant les avantages des matériaux organiques (molécule A) et inorganiques (métal B et halogène X). Très récemment, des cellules solaires à boîtes quantiques à bases de pérovskites purement inorganiques ont également montré des efficacités prometteuses, ce qui en fait une alternative potentiellement stable et efficace à leurs cousins hybrides.Le but de cette thèse de doctorat est d'étudier et de mieux comprendre les instabilités structurelles et thermodynamiques de ces pérovskites halogénées, avec un focus sur la pérovskite purement inorganique CsPbI3.Dans un premier temps les propriétés vibrationnelles et électroniques des différentes phases de CsPbI3 sont étudiées grâce à différentes techniques ab-initio, dont la plupart sont basées sur la théorie de la fonctionnelle de la densité (DFT) et son approche en réponse linéaire (DFPT). Alors que la phase γ noire, cruciale pour les applications photovoltaïques, se comporte de manière harmonique autour de l'équilibre, pour les trois autres phases nos calculs de phonons froids révèlent une instabilité de double puits au centre de la zone de Brillouin. Nos calculs montrent également que le terme d'entropie d'ordre-désordre lié à ce double puits est crucial pour empêcher la formation de la phase pérovskitoïde jaune. Nous analysons ensuite en détail les changements structurels et l’effet Rashba dynamique le long de trajectoires de dynamique moléculaire à la lumière de ces résultats.La seconde partie de la thèse porte sur la stabilité thermodynamique de la pérovskite hybride MAPbI3. Notre étude expérimentale par ellipsométrie apporte une meilleure compréhension de la décomposition chimique de MAPbI3 en ses deux précurseurs, l’iodure de méthylamonium et l'iodure de plomb, que nous avons prédite grâce à des calculs de diagrammes de stabilité DFT et que nous confirmons par diffraction des rayons X. Enfin, nous démontrons que la pérovskite hybride MAPbI3 se comporte davantage comme les composés inorganiques (grande constante diélectrique, faible énergie de liaison des excitons) que comme les matériaux organiques (faible constante diélectrique, forte énergie de liaison d'exciton)
Hybrid halide perovskites (ABX3) have emerged over the past five years as absorber layers for novel high-efficiency low-cost solar cells combining the advantages of organic (molecule A) and inorganic (metal B, halogen X) materials. Very recently, fully inorganic perovskite quantum dots also shown promising efficiencies, making them a potentially stable and efficient alternative to their hybrid cousins.The aim of this PhD thesis is to study and better understand both the structural and thermodynamic instabilities of these halide perovskites, with a specific focus on purely inorganic CsPbI3 structures.We first use various ab-initio techniques, the majority of which are based on Density Functional Theory (DFT) and its linear-response approach (DFPT), to investigate the vibrational and electronic properties of the different phases of CsPbI3. While the black γ-phase, crucial for photovoltaic applications, is shown to behave harmonically around equilibrium, for the other three phases frozen phonon calculations reveal a Brillouin zone center double-well instability. We also show that avoiding the order-disorder entropy term arising from these double-well instabilities is key in order to prevent the formation of the yellow perovskitoid phase, and evidence a Rashba effect when using the symmetry breaking structures obtained through frozen phonon calculations. We then analyze the structural changes and the dynamical Rashba splitting along molecular dynamics trajectories in the light of our findings.In a second phase, we investigate the thermodynamical stability of hybrid perovskite MAPbI3. Our experimental ellipsometry-based study brings better understanding of the chemical decomposition of MAPbI3 into its two precursors, methylammonium and lead iodides, which we predicted using DFT stability diagram calculations and which we confirm by X-Ray diffraction. Last, we prove that hybrid perovskite structure MAPbI3 behaves more like inorganic compounds (high dielectric constant, low exciton binding energy) than like organic materials (low dielectric constant, high exciton binding energy)

This project was a comprehensive study of interfacial and compositional engineering on perovskite solar cells (PSCs). Significantly enhanced power conversion efficiency and device lifetime of PSC photovoltaic technology were achieved by ion doping based on solution-processed and vapour-assisted treatments. The effects of various amine-contained ligands on enhancing performance of PSC were systematically investigated to reveal controlling defects and interfacial properties in the materials. This work provides several new insights into perovskite solar cells. The research outcomes benefit the development of PSCs based photovoltaic technology.