This research explores the wide range of potential applications of perovskite heterostructures (PHSs). Recently, researchers have made considerable progress in optoelectronic devices based on PHSs for energy-related and sensing applications. Here we begin by introducing the fundamental theory of PHS and focus on its optoelectronic properties. We focus on fabricating and characterizing advanced semiconducting heterostructure optoelectronics devices. The main objective of understanding their fundamental behavior is to tailor and improve their functionalities and empower different applications. Therefore, we propose the development of light management in photo detectors using the following scalable and cost-effective fabrication techniques: (i) The design of nano electronic and optoelectronic devices based on the layering of inorganic and organic hybrid Perovskite CH3NH3PbBr3/Molybdenum disulfide MoS2 single crystal. We developed a new method for stacking the n-type MoS2 single crystal with p-type Perovskite CH3NH3PbBr3 single crystal in the vertical direction, which enabled us to form a van der Waals heterojunction p–n diode. This demonstrates good current-voltage rectifying behavior in the dark and under light illumination. (ii) The use of inkjet-printed photo detectors using Graphene/Perovskite/Graphene (GPG) Heterostructures in the visible light region. This is achieved by fabricating a graphene/perovskite metal-semiconductor-metal (MSM) configuration through inkjet printing or by employing the hybrid approach (a combination of inkjet printing and transferred layers) as a high-gain visible light photo detector. This research opens a new path in the light management of optoelectronic devices.

Cette thèse s’inscrit dans la conjoncture actuelle de la recherche et du développement des matériaux pour les énergies renouvelables et dispositifs optoélectroniques à bas coût. Nous avons développées des nouveaux matériaux de pérovskites 2D et 3D afin d’exploiter leurs propriétés originales dans le but de les intégrer dans un second temps dans des dispositifs photoniques et photovoltaïques. Le travail d’ingénierie moléculaire sur la flexibilité des pérovskites 2D a permis de moduler le gap optique, d’extraire des informations sur les propriétés excitonique ainsi que l’activation de la photoluminescence. Quant à la flexibilité de la mise en forme des nouvelles pistes ont été initiées. L’étude de cette pérovskite 3D spécialement MAPI est très utile pour les applications photovoltaïques. La connaissance des propriétés optiques, structurales et de transport est une clé majeure pour l’augmentation des rendements et la stabilité de ces cellules / This thesis is involved in the current situation of research and development of materials for renewable energy and optoelectronic devices at low cost.We have developed new 2D and 3D perovskite materials to exploit their unique properties in order to integrate them in a second time in photonic and photovoltaic devices. The molecular engineering work on flexibility perovskites 2D allowed to modulate the optical gap, to extract information about the properties excitonqiue as well as activation of the photoluminescence. As to the flexibility of the layout of the new tracks were initiated.The study of this 3D perovskite especially MAPI is very useful for photovoltaic applications. The knowledge of the optical properties, structural and transport is a major key to increased yields and stability of these cells.

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.

<p>With increasing global renewable energy demands, there is a need for new materials with improved performance, lower cost, and less toxicity. One such application is photovoltaics, where halide perovskites (HaPs) represent the fastest growing market of absorbers owing to their impressive optoelectronic properties and excellent tunability from composition engineering and structural manipulation. However, the practically infinite composition-structure space of HaPs when considering cation and/or anion site mixing, octahedral distortion and rotation, and other forms of polymorphism, raise considerable challenges when comprehensively exploring their stability and optoelectronic properties. First principles calculations are powerful tools that can investigate large numbers of compounds and structures in a high-throughput fashion. </p><p>In my thesis, I performed high-throughput density functional theory (DFT) computations to generate a HaP dataset within a wide chemical space covering ~500 unique chemical compositions in the (pseudo-)cubic phase, across a 14-dimensional ionic space. This work explored both pure and alloyed compositions, with the latter simulated using the special quasi-random structures approach. Many critical properties were computed using the semi-local GGA-PBE and hybrid non-local HSE06 functionals, including decomposition and mixing energies, electronic band gap, and spectroscopic limited maximum efficiency (SLME), which is a theoretical surrogate for the likely absorption efficiency of the compound when used in a single-junction solar cell. Property screening over this dataset yielded 32 stable perovskite candidates with attractive optoelectronic properties.</p><p>Polymorphism in HaPs is investigated by simulating larger supercell alloys with different ionic ordering, generating compounds with random octahedral distortions and rotations, and optimizing various compositions in non-cubic phases such as tetragonal and orthorhombic. Linear correlation analysis is performed to gain a critical understanding of how properties are influenced by specific cations and anions, their mixing fractions, the perovskite phase, ionic clustering, and amount of strain or distortion in the lattice. Finally, trends, design rules, and predictive insights achieved from the DFT datasets are applied over a much larger set of thousands of hypothetical compounds, resulting in identification of more promising materials and understanding of the most important A-B-X combinations that yield multiple desired objectives.</p><p>Furthermore, a similar DFT workflow is applied for designing transition metal electrocatalysts. DFT simulations are performed to model Hydrogen adsorption, OH adsorption, and the water splitting reaction on Ni3N/Ni and Co2N/Co hybrid structures, to explore their likelihood in being used for Hydrogen Evolution Reaction (HER). The results reveal the excellent catalytic performance of transition metal and transition metal nitride hybrid structures.</p><p><br></p>

This dissertation is focused on ferromagnetic, multiferroics, and two-dimensional (2D) perovskites, exploring different unique collective magnetic and ferroic characters: (1) ferromagnetic thin film Co/Pd multilayers, (2) BaTiO3-BiFeO3 (BTO-BFO) a magneto-electric materials system, and (3) CuCl4 halide organic-inorganic perovskites. Low-power all-optical memory offers a unique opportunity to achieve ultra-fast magnetic switching in which the switching dynamics are not thermally mediated and occur on the order of the laser pulse. However, it is challenging to achieve a low-power optically excited magnetization precession angle above 90 degrees, which is required for magnetic switching. Co/Pd thin film multilayers were investigated for their potentially large perpendicular magnetic anisotropy (PMA) with three differing regimes of magnetic anisotropy: in-plane, weakly out-of-plane, and out-of-plane. Utilizing the time-resolved magneto-optical Kerr effect (TR-MOKE), we observed clear magnetic precession (on the order of a few GHz) with magnetic precession angle increasing (up to 4.5 degrees) for thinner Co samples which demonstrated stronger PMA. We observed a clear connection between PMA strength and precession amplitude as well as a large efficiency of energy transfer between spin and orbital subsystems for our strongest PMA sample. BTO-BFO is a strong room-temperature multiferroic with enhanced magneto-electric properties compared to BFO. We utilized time-resolved differential reflectivity (TR-DR) and TR-MOKE to observe strong coherent acoustic phonons in thin films as well as nanorods. Our nanorods showed additional modes (a new 20 GHz and 6 GHz mode) not observed in thin films including the fast 33 GHz mode which showed some weak tunability with high magnetic fields (up to 10 T). The observed tunability of these modes in an external magnetic field shows interesting coupling between magnetic moment and phononic modes which may be caused by the breaking of the spin-cycloid at the interface of the nanorods and the surface of the nanorods. We also observed second harmonic generation (SHG) emission which demonstrated a large enhancement in our nanorod structures with further observation of wavelength dependence. Finally, ferromagnetic resonance on our nanorod and thin film BTO-BFO structures indicated very weak Gilbert damping (on the order of 10−3), demonstrating the practicality of our structure for low-spin loss applications. Lastly, this dissertation focuses on a project around CuCl4 and CuCl2Br2 perovskites in which we observed time-dependent SHG. An increase in SHG as a function of infrared laser exposure is shown to coincide with changes in the crystal structure of the Cu perovskite materials. This increase in SHG was shown to last for a few days after hours of laser exposure indicating a slow hysteretic change to the crystal structure of the perovskites. / Doctor of Philosophy / Multifunctionality in materials is important for various applications including future mem- ory devices where ferromagnetism (collective magnetic order), ferroelectricity (collective electric polarization order), and piezoelectricity (collective strain order) can be implemented in a given device. This dissertation centers on three material systems for exploring ferroic orders: Co/Pd thin multilayers, BaTiO3-BiFeO3 (BTO-BFO) films and nano-rod arrays, and Cu halide organic-inorganic perovskite thin films and 2D structures. Co/Pd thin films demonstrate interesting ferromagnetic order with magnetic anisotropy in which the magnetization of the thin film has a preferred direction based on the thickness of the thin film. BTO-BFO demonstrates coupling between ferroelectric and antiferromagnetic order. The magnetic information may be controlled by applying electric fields or strain and Cu halide perovskites demonstrate potentially created ferroelectric order under long-term laser expo- sure with high ferroelectric switching speeds. Dynamics and nonlinear optical responses in these materials systems were explored with Ti:Sapphire pulsed lasers (∼ 100 fs). Our techniques allowed us for a better understanding of fast carrier and spin dynamics after optical excitation. Furthermore, nonlinear optics, in which two or more photons can be used to emit higher energy photons, were employed to explore the ferroelectric properties within these material systems. The results presented in this dissertation provided information on collective orders and fundamental interactions in several less-explored material systems.

Metal halide perovskites (MHPs) have attracted the attention of researchers particularly in the photo-absorption field. These materials rival traditional semiconductors with their cost-effective ease of synthesis, tunable bandgaps, and excellent photophysical properties. Single-junction MHP solar cells have rivaled current silicon-based photovoltaic devices, boasting a 25.2% light absorption conversion. Recently, MHPs have proven to be effective in x-ray detection. In this paper an investigation of three titanium-based MHPs was conducted. The goal of this research was to characterize the MHPs and determine if they are feasible materials to incorporate in x-ray detectors. After completing the research, two MHP species, FA2TiI6 and MA3TiCl7, were able to be synthesized and characterized. Their crystal systems were determined to be tetragonal with a P4/mmm space group. However, due to equipment limitations, their feasibility in x-ray detectors could not be determined.

Wide bandgap perovskites are emerging as suitable candidates for the technology of tandem solar cells. Understanding their optical properties is a prerequisite for improving the corresponding solar cells’ efficiencies. In this thesis, we employ various steady-state spectroscopies to reveal the optical properties of two wide bandgap perovskites: FA0.83Cs0.17Pb(I0.7Br0.3)3 or PVK1 and FA0.83Cs0.17Pb(I0.5Br0.5)3 or PVK2. The optical properties of interest are the semiconductors’ absorption spectra, the sub-bandgap absorption features, the bandgap energy, the Urbach energy, and the excitonic binding energy. We find that the sub-bandgap absorption can be characterized by a single exponential function. We also find that the Urbach energies and the excitonic binding energies are below the thermal energy at room temperature, which signals that PVK1 and PVK2 are excellent nominees for photovoltaic absorbers. Finally, the bandgap energy is red shifted due to excitonic effects as revealed by the Elliot model.

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