Highly efficient and stable planar perovskite solar cells by solution-processed tin oxide

Perovskite solar cells (PSCs) are one of the most promising lab-scale technologies to deliver inexpensive solar electricity. Low-temperature planar PSCs are particularly suited for large-scale manufacturing. Here, we propose a simple, solution-processed technological approach for depositing SnO2 layers. The use of these layers in planar PSCs yields a high stabilized power conversion efficiency close to 21%, exhibiting stable performance under real operating conditions for over 60 hours. In addition, this method yielded remarkable voltages of 1214 mV at a band gap of 1.62 eV (approaching the thermodynamic limit of 1.32 V) confirming the high selectivity of the solution-processed layers. PSCs aged under 1 sun illumination and maximum power point tracking showed a final PCE of 20.7% after ageing and dark storage, which is slightly higher than the original efficiency. This approach represents an advancement in the understanding of the role of electron selective layers on the efficiency and stability of PSCs. Therefore, the newly proposed approach constitutes a simple, scalable method paving the way for industrialization of perovskite solar cells.

Formation of High-Performance Multi-Cation Halide Perovskites Photovoltaics by delta-CsPbI3/delta-RbPbI3 Seed-Assisted Heterogeneous Nucleation

Essa Awadh R Alharbi, Masaud Hassan S Almalki, Thomas Paul Baumeler, Felix Thomas Eickemeyer, Ulf Anders Hagfeldt, Anurag Krishna, Mounir Driss Mensi, Olivier Ouellette, Linfeng Pan, Zaiwei Wang, Bowen Yang, Shaik Mohammed Zakeeruddin

The performance of perovskite solar cells is highly dependent on the fabrication method; thus, controlling the growth mechanism of perovskite crystals is a promising way towards increasing their efficiency and stability. Herein, a multi-cation halide composition of perovskite solar cells is engineered via the two-step sequential deposition method. Strikingly, it is found that adding mixtures of 1D polymorphs of orthorhombic delta-RbPbI3 and delta-CsPbI3 to the PbI2 precursor solution induces the formation of porous mesostructured hexagonal films. This porosity greatly facilitates the heterogeneous nucleation and the penetration of FA (formamidinium)/MA (methylammonium) cations within the PbI2 film. Thus, the subsequent conversion of PbI2 into the desired multication cubic alpha-structure by exposing it to a solution of formamidinium methylammonium halides is greatly enhanced. During the conversion step, the delta-CsPbI3 also is fully integrated into the 3D mixed cation perovskite lattice, which exhibits high crystallinity and superior optoelectronic properties. The champion device shows a power conversion efficiency (PCE) over 22%. Furthermore, these devices exhibit enhanced operational stability, with the best device retaining more than 90% of its initial value of PCE under 1 Sun illumination with maximum power point tracking for 400 h.

WILEY-V C H VERLAG GMBH2021

Compositional and interfacial optimization for enhancement of perovskite solar cells performance

Essa Awadh R Alharbi

Non-renewable sources are responsible for most of the overall greenhouse gas emissions, the development of sustainable energy sources is of prime importance to mitigate the negative effects of climate change. Among renewable sources, solar energy is one of the most abundant forms of energy available. Perovskite photovoltaics has emerged as one of the promising candidates for harvesting solar energy. However, these perovskite solar cells suffer from instability which is primarily due to the bulk and interface defects. In this thesis, we focus on the passivation of the bulk and interface defects to enable high-performance and stable devices. At the beginning of the thesis, we engineered the composition of mixed-cation and mixed-halide perovskite films by judicious incorporation of guanidinium iodide to suppress the parasitic charge carrier recombination, which enabled the fabrication of >20% efficient and operationally stable PSCs yielding reproducible photovoltage as high as 1.20 V. Thereafter, in our next project, we develop a facile strategy to reduce the level of electronic defects present at the interface between the perovskite film and the hole transport layer by treating the perovskite surface with different types of ammonium salts, namely ethylammonium, imidazolium, and guanidinium iodide. We find that this treatment boosts the power conversion efficiency from 20.5% for the control to 22.3%, 22.1%, and 21.0% for the devices treated with ethylammonium, imidazolium, and guanidinium iodide, respectively. Best performing devices showed a loss in efficiency of only 5% under full sunlight intensity with maximum power tracking for 550 h. We employed 2D-solid-state NMR (1H-1H correlation) spectroscopy to unravel the atomic-level mechanism of this passivation effect. Following that, we applied a facile and very effective method that employs methylammonium triiodide (MAI3) for bulk passivation together with interface passivation developed in the second project for holistic defect mitigation in perovskite solar cells. As a result, the champion device shows a power conversion efficiency (PCE) of 23.46% with a high fill factor (FF) of over 80%. Furthermore, these devices exhibit enhanced operational stability, with the best device retaining ~ 90% of its initial PCE under 1 Sun illumination with maximum power point tracking for 350 h. Finally, in our last project, we reconfigured the design of the alkylammonium halide salts to create a holistic bulk and interface engineering. We show that dimethylammonium head along with octyl chain and iodide counter anion works best in the bulk whereas dimethylammonium head along with octyl chain and fluoride counter anion works best at the interface. With a synergistic combination of both bulk and surface passivation, we achieved a high PCE of 24.91% along with exceptional long-term operational stability. In summary, in this thesis we employed different strategies based on organic ammonium salts to engineer the bulk and interface of the PSCs. We did an in-depth investigation of the optoelectronic properties, local structure, and molecular interactions with a combination of characterization at different length and time scales. Our results show that it is imperative to passivate both bulk and interface defects for obtaining high efficiency and stable solar cells. From our work, one can take inspiration from the design and analysis of new materials for the passivation of the PSCs.

EPFL2022

Formation and stabilization of all-inorganic perovskites for photovoltaics

Zaiwei Wang

All-inorganic perovskite films hold promise for improving stability of perovskite solar cells. However, the desirable narrow-bandgap inorganic perovskites (such as CsPbI3 and CsPbI2Br) are suffering from the thermodynamic phase instability, as the photoactive black phase (Î±, Î², or Î³ phase) spontaneously transforms into a more thermodynamically stable yellow phase (ÎŽ-phase) in ambient condition, which is limiting the further development of high-performance inorganic PSCs. The stabilization of black phase and the formation of high-quality perovskite films are promoting the remarkable progress for the performance and stability of inorganic perovskite solar cells. Firstly, we show that europium doping of CsPbI2Br stabilizes the black phase of narrow band gap inorganic perovskite at room temperature. We rationalize it by using solid-state nuclear magnetic resonance and high-angle annular dark-field scanning transmission electron microscopy, which show that europium is incorporated into the perovskite lattice. We demonstrate a power-conversion efficiency (PCE) of 13.71% for an inorganic PSC with the composition CsPb0.95Eu0.05I2Br perovskite. Stability tests show that the devices retain 93% of the initial efficiency after 370 hours under maximum power point tracking measurement. Secondly, we demonstrate a function of dopants by adding barium in CsPbI2Br. We find that barium is not incorporated into the perovskite lattice but induces phase segregation, resulting in a change in the iodide/bromide ratio compared to the precursor stoichiometry and consequently a reduction in the band gap energy of the perovskite phase. The device with 20 mol% barium shows a high PCE of 14.0% with a high open-circuit voltage (Voc) of 1.33 V. Then we propose an intermediate-phase engineering strategy to improve the inorganic perovskite/metal oxide interface by utilizing volatile salts. The introduction of organic cations (such as methylammonium and formamidinium), which can be doped into the perovskite lattice, leads to the formation of an organic-inorganic hybrid perovskite intermediate phase, promoting a robust interfacial contact through hydrogen bonding. A champion CsPb(I0.75Br0.25)3-based device with a PCE of 17.0% and a Voc of 1.34 V was realized. Last, the intermediate phase engineering strategy is reported to promote the pure ÃÂ³-phase CsPbI3 perovskite film formation. According to the investigation of the phase transformation processes of pure CsPbI3 and that with different additives, including NH4I, BAI, MAI, FAI and DMAI, we found that the formation of a 3D organic-inorganic hybrid perovskite intermediate phase is essential to avoid the generation of undesired yellow phase and promote the formation of pure black-phase CsPbI3 film. A champion PCE of 17.70% with a stabilized power output of 17.58% based on the optimized CsPbI3-DMAI device is achieved. Overall, we investigate two possible scenarios for element doping: (1) the dopants are incorporated into the crystal lattice for the improvement of stability and efficiency of inorganic PSCs; (2) the dopants form separate phases to induce the halide phase segregation and suppress non-radiative recombination of perovskite films. Besides, based on the formation of 3D organic-inorganic perovskite intermediate phase, we not only promote the formation of pure black phase CsPbI3, but also promotes a robust interfacial contact of inorganic perovskite and metal oxide transport layers.