Compositional Engineering of Perovskite Light Absorbers for Enhanced Stability and Performance through 2D/3D Interfacing

The semiconducting hybrid-organic inorganic halide perovskites have excellent optical and electronic properties that attract the interest of scientists and researchers. Perovskite solar cells have seen the most rising-rate in the chart of solar cell efficiency from 3 to over 25% in less than ten years. In the last three years, most researchers have been focusing on the Î±-FAPbI3-based perovskite solar cells due to having a lower bandgap (1.45 eV) which is closer to the Shockley-Queisser optimum (1.1- 1.4eV) to gain high efficiency. A distinctive feature of FAPbI3 is that it is more thermally stable compared to MAPbI3. However, the Î±-FAPbI3 perovskite is not stable at room temperature as it converts to the undesirable ÎŽ-phase. The 2D- Ruddlesden-Popper-phase-doped 3D FAPbI3 enhancing the stability of the structure, albeit the bandgap is increased rendering a less optimal bandgap. The main achievement of this thesis is discovering that the doping of FAPbI3 with large alkyl ammonium moieties enhances efficiency and stability while maintaining the bandgap of pure Î±-FAPbI3 perovskite phase. I describe the resulting composition by the formula (A)xFAPbI3, where A represents the large alkyl ammonium iodide species. I study the stabilization of Î±-FAPbI3 via doping with 5-amino valeric acid hydroiodide (AVAI). By using solid-state NMR, we demonstrate the atomic-level interaction between this molecular modulator and the perovskite lattice and propose a structural model of the stabilized three-dimensional structure, further aided by density functional theory (DFT) calculations. We find the presence of AVAI produces highly crystalline films with large, micrometer-sized grains and enhanced charge-carrier lifetimes, as probed by transient absorption spectroscopy. Optical measurements confirm that there is no effect on the bandgap of FAPbI3 after doping. The devices based on (AVAI)0.25FAPbI3 exhibit superior operational stability in comparison with neat FAPbI3 while achieving power conversion efficiency of 19%. A similar approach based on benzylammonium iodide (BzI) has been used. The structural and optical characterization of films based on (BzI)xFAPbI3 composition demonstrate that there is no 2D phase forming under these conditions. Moreover, solid-state NMR results show BzI interacting on the atomic level with Î±-FAPbI3 by binding to the 3D perovskite through hydrogen bonding interaction and stabilizing it against the detrimental Î±-to-ÎŽ phase transition. Perovskite solar cells based on the (BzI)0.25FAPbI3composition achieve power conversion efficiencies exceeding 20%, which is accompanied by enhanced shelf-life and operational stability, maintaining 80% of the performance after one year at ambient conditions.Finally, films based on (BzI)0.25FAPbI3 compositions are further investigated upon aging under the ambient conditions, as they show an unexpected transition from black to red color without transition to expected yellow ÎŽ phase, unlike the reference FAPbI3. I perform different measurements to investigate the nature of this red phase as a function of annealing temperature compare these properties to the corresponding Ruddlesden-Popper phase (Bz2FAn-1PbnI3n+1). The red phase was found to be a mixture of a 2D phase (n = 2) Bz2FAPb2I7 and ÎŽ-FAPbI3, which acts as a barrier to the Î±-to-ÎŽ phase transition.

Intermediate Phase Enhances Inorganic Perovskite and Metal Oxide Interface for Efficient Photovoltaics

Anand Agarwalla, Claudia Esther Avalos, Brian Irving Carlsen, David Lyndon Emsley, Wei Guo, Ulf Anders Hagfeldt, Dominik Józef Kubicki, Yuhang Liu, Haizhou Lu, Aditya Mishra, Mona Shasti, Wolfgang Richard Tress, Zaiwei Wang, Zishuai Wang, Wanchun Xiang, Jiahuan Zhang

Interfacial modification is crucial to fully develop the potential of semiconductor devices, including the revolutionary halide perovskite-based optoelectronics, such as photovoltaics, light-emitting diodes, and photodetectors. The all-inorganic halide perovskites, which are potential long-term stable photovoltaic materials, are suffering from poor interfacial contact with metal oxide charge-selective layer, severely limiting the power conversion efficiency and stability of inorganic perovskite solar cells. Here, 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 power conversion efficiency of 17.0% and an open-circuit voltage of 1.34 V was realized, implying that a record of over 65% of the Shockley-Queisser efficiency limit is achieved.

CELL PRESS2020

Goldschmidt's Rules and Strontium Replacement in Lead Halogen Perovskite Solar Cells: Theory and Preliminary Experiments on CH3NH3SrI3

Ulf Anders Hagfeldt, Tor Jesper Jacobsson

During the past few years, organic lead halogen perovskites have emerged as a class of highly promising solar cell materials, with certified solar cell efficiencies now surpassing 20%. Concerns have, however, been raised about the possible environmental and legalization problems associated with a new solar cell technology based on a water-soluble lead compound. Replacing lead in the perovskite structure: with a less toxic element, without degrading the favorable photo physical properties, would therefore be of interest. In this paper, the possibility of replacing lead with other metal ions is explored by following the replacement rules of Goldschmidt together with additional quantum mechanical considerations. This analysis provides a conceptual toolbox toward replacing lead, as well as additional insights into the photo physics of the metal halogen perovskites. This approach is exemplified by focusing on strontium in particular, which is nontoxic and relatively inexpensive. The ionic radius of Sr2+ and Pb2+ are almost identical, suggesting an exchange could be made without affecting the crystal structure. Couple cluster calculations on the metal ions and their halogen salts give the bonding patterns to be sufficiently similar and density functional theory (DFT) revealed the strontium perovskite, CH3NH3SrI3, to be a stable phase, despite the difference in electronegativity between lead and strontium. This is further supported by the existence of binary PM, and SrI2 compounds and the beneficial formation energy of the strontium perovskite. The electronic properties of both CH3NH3SrI3 and CH3NH3PbI3 were simulated and compared, revealing a higher degree of ionic interaction in the metal halogen bound in the strontium perovskite. This is a consequence of the lower electronegativity of strontium, which, together with the lack of d-orbitals in the Valence of Sr2+, results, in a higher band gap. The band gap for the strontium perovskite was estimated to 3.6 eV, which unfortunately is too high for an efficient photo absorber. Initial investigations on experimental synthesis of the strontium perovskite, using wet chemical methods, revealed it to be harder to produce than the lead perovskite This is explained as a:consequence of different bonding patterns in the metal iodine salts, which obstruct the methylammonium intercalation pathway utilized for forming the perovskite. Vapor phase methods are instead suggested as more promising synthesis routes.

American Chemical Society2015

Surface, Interface, and Bulk Electronic and Chemical Properties of Complete Perovskite Solar Cells: Tapered Cross-Section Photoelectron Spectroscopy, a Novel Solution

Thomas Mayer, Mohammad Khaja Nazeeruddin, Iwan Zimmermann

The surface, interface, and bulk properties are a few of the most critical factors that influence the performance of perovskite solar cells. The photoelectron spectroscopy (PES) is used as a technique to analyze these properties. However, the information depth of PES is limited to 10-20 nm, which makes it not suitable to study the complete devices, which have a thickness of similar to 1 mu m. Here, we introduce a novel and simple technique of PES on a tapered cross section (TCS-PES). It provides both lateral and vertical resolutions compared to the conventional PES so that it is suitable to study a complete perovskite solar cell. It offers many benefits over conventional PES methods such as the chemical composition in the micrometer scale from the surface to the bulk and the electronic properties at the multiple interfaces. The chemical natures of different layers of the perovskite-based solar cells [(FAP-bI(3))(0.85)(MAPbBr(3))(0.15)] can be identified precisely for the first time using the TCS-PES method. We found that the perovskite layer has higher iodine concentration at the Spiro/perovskite interface and higher bromine concentration at the TiO2/perovskite interface. UPS measurements on the tapered cross section revealed that the perovskite is n-type, and the solar cell studied here is a p-n-n structure type device. The unique possibilities to analyze the complete solar cell by XPS and UPS allow us to estimate the band bending in a working solar cell. Moreover, this technique can further be used to study the device under operating conditions, and it can be applied in other solid-state devices like solid electrolyte Li-ion batteries, LEDs, or photoelectrodes.

AMER CHEMICAL SOC2020

Goldschmidt's Rules and Strontium Replacement in Lead Halogen Perovskite Solar Cells: Theory and Preliminary Experiments on CH3NH3SrI3

Ulf Anders Hagfeldt, Tor Jesper Jacobsson

American Chemical Society2015