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Recently, perovskite solar cells (PSC) with high power-conversion efficiency (PCE) and long-term stability have been achieved by employing 2D perovskite layers on 3D perovskite light absorbers. However, in-depth studies on the material and the interface between the two perovskite layers are still required to understand the role of the 2D perovskite in PSCs. Self-crystallization of 2D perovskite is successfully induced by deposition of benzyl ammonium iodide (BnAI) on top of a 3D perovskite light absorber. The self-crystallized 2D perovskite can perform a multifunctional role in facilitating hole transfer, owing to its random crystalline orientation and passivating traps in the 3D perovskite. The use of the multifunctional 2D perovskite (M2P) leads to improvement in PCE and long-term stability of PSCs both with and without organic hole transporting material (HTM), 2,2′,7,7′-tetrakis-(N,N-di-p-methoxyphenyl-amine)-9,9′-spirobifluorene (spiro-OMeTAD) compared to the devices without the M2P.

Faced with the growing demands for energy in modern society, organic-inorganic metal halide perovskite materials have recently fascinated the photovoltaics (PV) research community due to a combination of their high quality optoelectronic properties and their ease in the fabrication proceed. As a result, solar cells employing the perovskite materials have been researched exponentially on their way and now the power conversion efficiency (PCE) of perovskite solar cells have been improved over 23% since the first report showing the PCE of 3% in 2009. In this thesis, I investigate compositional modification of perovskite materials and optimization of the charge transporting materials to produce high efficiency, stable and reproducible perovskite solar cells. First of all, after the reasonable performance was achieved, we have innovated a new approach of interface engineering in a perovskite layer to boost efficiency of devices. Engineering a compositional gradient with formamidinium bromide (FABr) at the rear interface between a pristine mixed perovskite ((FAPbI3)0.85(MAPbBr3)0.15) film and a hole transporting material (spiro-OMeTAD) demonstrated that charge collection is improved and charge recombination is reduced at the interface, which leads to a striking enhancement in open-circuit voltage (VOC). This result shed light on the importance of the passivation engineering on the rear surface of perovskite layers. However, beyond the improvement of efficiency, a long-term stability under moisture and continuous illumination is still remained as another challenge for market deployment of the perovskite solar cells. To develop the stability, we have developed the engineering by the surface growth of a two-dimensional (2D) perovskite, the crystal structure of A2BX4, on top of a bulk three-dimensional (3D) perovskite ABX3 film. It is well-known that the 2D perovskite has the superior stability, but suffered because of their low efficiency in the application of photovoltaics. The formation of a distinct 2D perovskite on top of the 3D perovskite (Cs0.1FA0.74MA0.13PbI2.48Br0.39) layer was proved by investigation of structural and optical properties of the stack. This embodying two different type of perovskite layer in one film had never been shown. Finally, this innovative approach led to the PCE of 21% and enhanced stability sustaining 85% of the initial value after 800 hours under full illumination. Thus, my approach of coating 2D perovskite layer make the perovskite solar cells more effective and stable for commercialization. Besides, to avoid the toxic chemical the lead free perovskite (Cs2AgBiBr6) was explored as photovoltaics and the further improvement can be expected. The last results presented in this thesis are related to optimization of the electron transporting layer (ETL) and hole-transporting materials (HTM) for efficient perovskite solar cells. It is shown that the ETL and the HTMs are playing a significant role in realizing efficient and stable perovskite solar cells.

By two‐step sequential Pb2+ adsorption and reaction with methylammonium‐iodide (MAI) or ‐bromide (MABr) at a low concentration level of 0.06–0.10 m over mesoporous TiO2 or ZrO2 film, a well‐defined nanoscale CH3NH3PbI3 (MAPbI3) photosensitizer or CH3NH3PbBr3 (MAPbBr3) light emitter could be prepared in situ, respectively in a reproducible and atom‐economical way. The as‐prepared nanoscale perovskites are compared with their thin film counterparts in terms of light absorption/emission, crystallinity, surface morphology, and energy‐conversion efficiency. The nanoscale perovskite‐decorated films display more transparency than the bulky film due to the much lower amount deposited, while blueshifted and overwhelmingly brighter photoluminescence is observed in the “nano” relative to the “bulk” due to quantum size confinement. Transmission electron microscopy images also clearly show that a few nanometer‐sized perovskite dots are deposited homogeneously over the surface of TiO2‐ or ZrO2‐particulate film in the course of the current preparative route. When the nano‐MAPbI3 is tested as a photosensitizer in a solid‐state dye‐sensitized solar cell configuration with a very thin (≈650 nm) TiO2 mesoporous film, it has a promising initial power conversion efficiency of 6.23%, which outperformed the result of 2.28% from a typical organic molecular dye coded as MK‐2.

Although 2D|3D has shown potential for application in multifunctional devices, the principle of operation for multifunction devices (SOLAR Cell-LED: SOLED) has not yet been revealed. However, most studies have reported that the devices have only one auspicious characteristic. Here in this study the SOLED devices are monitored and investigated in a 2D|3D heterostructure with a multidimensional perovskite. It is fond that a 2D|3D heterostructure with a multidimensional perovskite interface induces carrier transmission from the interface, increasing the density of electrons and holes, and increasing their recombination. An interface-engineered perovskite 2D|3D-heterojunction structure is employed to realize the multifunctional photonic device in on-chip, exhibiting overall power conversion efficiencies of photovoltaics up to 21.02% under AM1.5, and external quantum efficiency of the light-emitting diode up to 5.13%. This novel phenomenon is attributed to carrier transfer resulting in a high carrier density and enhanced carrier recombination at the 2D|3D interface.

Intercalated and unmodified TiS2 nanomaterials were synthesized and characterized by UV-Visible-NIR spectroscopy, Powder X-Ray Diffraction, and X-Ray Photoelectron and Ultraviolet Photoelectron Spectroscopy. Photoelectron spectroscopy measurements indicated that CoS and Cu2S appeared to be intercalated between sheets of partially or fully oxidized TiS2, which could be solution processed on conductive oxide substrates. The materials were then applied toward water oxidation and evaluated by cyclic voltammetry, chronoamperometry, and impedance measurements. While unmodified TiS2 was not observed to perform well as an electrocatalyst with overpotentials >3 V in 1 M NaOH electrolyte, CoS intercalation was found to lower the overpotential by ∼1.8-1.44 V at 10 mA/cm2. Conversely, Cu2S intercalation resulted in only a modest increase in performance (>2.3 V overpotential). Impedance measurements indicated that intercalation increased the series resistance in the as-prepared samples but decreased the series resistance in oxidized samples.

Nanoscale CH3NH3PbI3 perovskite sensitizers are grown by delivering each precursor successively onto the surface of mesoporous (meso) TiO2 electrodes. Using Pb(NO3)(2) ions as a lead(II) source and CH3NH3I (MAI) for methylammonium and iodide sources, repetitive cycles of the two dipping steps are successful in growing few nanometer-sized MAPbI(3) gradually on the TiO2 surface inside the meso-TiO2 film. However, some aggregates are observed on the top surface of the meso-TiO2 film due to slight dissolution of PbI2 and its accumulation/reaction with MAI at the top surface of the meso-TiO2 film. To solve this inhomogeneity of the deposition, a nondestructive multiple deposition route for nanoscale MAPbI(3) is suggested as a successive precursor layer adsorption and reaction (SPLAR) process where, from the second cycle of deposition, PbI2 is delivered with the help of an ionic liquid compound dissolved in dichloromethane. With this new Pb precursor in less-polar solvents, nanoscale MAPbI(3) sensitizers are grown without dissolution of preformed perovskites or formation of some aggregates at the top surface. After the third cycle of SPLAR deposition, about 7.0 nm-sized MAPbI(3) sensitizers are prepared and display enhanced photovoltaic performance (7.18 +/- 0.31%) compared with devices obtained from only one cycle (5.74 +/- 0.30%).

Hybrid perovskite solar cells have been capturing an enormous research interest in the energy sector due to their extraordinary performances and ease of fabrication. However, low device lifetime, mainly due to material and device degradation upon water exposure, challenges their near-future commercialization. Here, we synthesized a new fluorous organic cation used as organic spacer to form a low-dimensional perovskite (LDP) with an enhanced water-resistant character. The LDP is integrated with three-dimensional (3D) perovskite absorbers in the form of MA(0.9)FA(0.1)PbI(3) (FA = NH2CH = NH2+, MA = CH3NH3+) and CS(0.1)FA(0.74)MA(0.13)PbI(2.48)Br(0.39). In both cases, a LDP layer self-assembles as a thin capping layer on the top of the 3D bulk, making the perovskite surface hydrophobic. Our easy and robust approach, validated for different perovskite compositions, limits the interface deterioration in perovskite solar cells yielding to >20% power conversion efficient solar cells with improved stability, especially pronounced in the first hours of functioning under environmental conditions. As a consequence, single and multijunction perovskite devices, such as tandem solar cells, can benefit from the use of the waterproof stabilization here demonstrated, a concept which can be further expanded in the perovskite optoelectronic industry beyond photovoltaics.